IAOe?IIAEUeIA AEAAeAI?ss IAOE OE?A?IE

?INOEOOO O?CE*II? O?I?? ?i. E.A.IENA?AEAANUeEIAI

____________________________________________________________________

EAIIAEA ss?ineaa Aeieo?iae*

OAeE 541.49:546.56, 546.73, 546.74

?AAeIEN-?aaeoe?? oao?aaiiaeueieo eiiieaen?a i?eaeth(III,II),
iiae?(III,II) oa eiaaeueoo(III,II) c IIE?AeAIOAOIEIE

acioai?nieie e?aaiaeaie

02.00.01 — iai?aai?/ia o?i?y

Aaoi?aoa?ao

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

aeieoi?a o?i?/ieo iaoe

EE?A — 1998

Aeena?oaoe??th ? ?oeiien

?iaioa aeeiiaia a ?inoeooo? o?ce/ii? o?i?? ?i. E.A.Iena?aeaanueeiai
Iaoe?iiaeueii? aeaaeai?? iaoe Oe?a?ie

Iaoeiaee eiinoeueoaio: aeaaeai?e IAI Oe?a?ie, aeieoi? o?i?/ieo iaoe,
i?ioani?

ssoeeie?nueeee Einoyioei Ai?eniae/

?OO IAI Oe?a?ie, ?aaeiee i?e aee?aeoe??

Io?oe?ei? iiiiaioe: /eai-ei?aniiiaeaio IAI Oe?a?ie, aeieoi? o?i?/ieo
iaoe,

i?ioani? Neiaiaeyiee Ieeiea Naiaiiae/

Ee?anueeee oi?aa?neoao ?i. Oa?ana Oaa/aiea,

aeaeai o?i?/iiai oaeoeueoaoo

aeieoi? o?i?/ieo iaoe, i?ioani?

Ouei?oeo Aaeaioei Aiaoie?eiae/

?inoeooo o?i?? iiaa?oi? IAI Oe?a?ie

caa?aeoaa/ a?aeae?eii

aeieoi? o?i?/ieo iaoe, noa?oee iaoeiaee ni?a?ia?oiee

Eaeue/aiei A?oae?e ?aaiiae/

?inoeooo i?aai?/ii? o?i?? IAI Oe?a?ie

caa?aeoaa/ a?aeae?eii

I?ia?aeia onoaiiaa: ?inoeooo caaaeueii? oa iai?aai?/ii? o?i?? ?i.

A.?.Aa?iaaenueeiai IAI Oe?a?ie, i. Ee?a

Caoeno a?aeaoaeaoueny “ _6__”__ea?oiy_______ 1999 ?ieo i
___14.00__aiaeei? ia can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee
Ae26.190.01 a ?inoeooo? o?ce/ii? o?i?? ?i. E.A.Iena?aeaanueeiai IAI
Oe?a?ie ca aae?anith: 252039, Ee?a-39, i?iniaeo Iaoee 31.

C aeena?oaoe??th iiaeia iciaeiieoenue a a?ae?ioaoe? a ?inoeoooo o?ce/ii?
o?i?? ?i. E.A.Iena?aeaanueeiai IAI Oe?a?ie ca aae?anith: 252039,
Ee?a-39, i?iniaeo Iaoee 31.

Aaoi?aoa?ao ?ic?neaiee “_5___” __aa?aciy___ 1999 ?ieo.

A/aiee nae?aoa?

Niaoe?ae?ciaaii? a/aii? ?aaee Aiaiie/ O.I.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. Iaei??th c oa?aeoa?ieo ?en no/anii? o?i?? ?
c?inoath/a aeei?enoaiiy eii?aeeiaoe?eieo niieoe (eiiieaen?a iaoae?a) a
i?ioeanao, ye? oi?iaeueii a?aeiinyoueny aei ?ioeo iaeanoae oe??? iaoee
(iai?., eaoae?oe/ieo — iaoaeieiiieaeniee eaoae?c, i?aai?/ieo — oaiieaoi?
i?ioeane ? o.i.). Oaea canoinoaaiiy eiiieaen?a iaiiaeeeaa aac
anoaiiaeaiiy aca?iica’yceo i?ae aaiiao?e/iith oa aeaeo?iiiith aoaeiaith
eii?aeeiaoe?eieo niieoe c iaeiiai aieo, oa ?o aeanoeainoyie — c ?ioiai.
Iaeiae aenia?eiaioaeueia ?aae?caoe?y oeueiai i?aeoiaeo /anoi
iaooiaoo?oueny ia a?aenooi?noue a?aeiia?aeiiai ani?oeiaioo ii??aeiaieo
eiiieaen?a c iiaeeeainoyie oe?ieiai aa??thaaiiy ?o oa?aeoa?enoee.

Eii?aeeiaoe?ei? niieoee ia?ao?aeieo iaoae?a, ooai?ai? acioai?nieie
iie?aeaioaoieie e?aaiaeaie (a ia?oo /a?ao oao?aacaiae?ioeeeeaie),
i?aaenoaaeythoue oi?eaeueio iiaeeea?noue aeey ae??oaiiy aeaiiai ieoaiiy,
ine?eueee oa?aeoa?ecothoueny oe?ieei no?oeoo?iei ??ciiiai?ooyi oa
iathoue ieceo niaoeeo?/ieo aeanoeainoae — aenieo oa?iiaeeiai?/io
no?ee?noue, e?iaoe/io ?ia?oi?noue oa caeaoi?noue noaa?e?coaaoe
iao?aaeeoe?ei? nooiai? ieeniaiiy iaoae?a. Iiaeeea?noue i?aoethaaoe c
aeaieie ?aaaaioaie a ianooaa? ?aaeueiiai /ano noaea iiaooi?i noeioeii
aeey aea/aiiy e?iaoe/ieo ia?aiao??a ?o ?aaeien-?aaeoe?e. E??i oiai,
aaaaoi acaiae?ioeeee?/ieo eiiieaen?a i?iyaeee ia?niaeoeai?
?aaeien-eaoae?oe/i? aeanoeaino?, oiio ?ioa?an aei ?o
ieenithaaeueii-a?aeiiaethaaeueieo oa?aeoa?enoee ? oe?eeii c?icoi?eei.

Aiae?c e?oa?aoo?ieo aeaieo aeicaiey? eiinoaooaaoe, ui iaeiie/ai?
a?aeiiino? i?i ?aaeien-oa?aeoa?enoeee oao?aaiiaeueieo eiiieaen?a
ia?ao?aeieo iaoae?a ? ianenoaiaoe/ieie, ui ?iaeoue i?iaeaiaoe/iei
anoaiiaeaiiy aca?iica’yceo i?ae aoaeiaith aeaieo niieoe ? ?o
aeanoeainoyie. A na?oe? oeueiai nenoaiaoe/ia aeine?aeaeaiiy
oa?iiaeeiai?/iiai ? e?iaoe/iiai aniaeo?a ?aaeien-iiaaae?iee eiiieaen?a
ia?ao?aeieo iaoae?a c iie?aeaioaoieie acioai?nieie e?aaiaeaie ?
aacoiiaii aeooaeueiei ieoaiiyi.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, oaiaie, ieaiaie. ?iaioa
i?iaiaeeeanue a ?aieao a?aeii/i? oaiaoeee a?aeae?eo ?5 ?inoeoooo
o?ce/ii? o?i?? ?i. E.A.Iena?aeaanue-eiai IAI Oe?a?ie ca i??i?eoaoieie
iai?yieaie “Aea/aiiy aoaeiae, no?eeino? ? ?aaeien-aeanoeainoae
iaoaeii?ioa?i?a oa eiiieaen?a, ui iiaeaeththoue ?o aeoeai? oeaio?e”,
“Iiea-eoey?ii-i?aai?ciaai? nenoaie ca o/anoth eii?aeeiaoe?eieo niieoe
d-iaoae?a” (? Aea?ae?a?no?aoe?? 0196U008221), “Aaoa?iaaii? ?aaeoe??
eii?aeeiaoe?eieo niieoe c aeieia?/ii aaaeeeaeie ?iiaie iaoae?a oa iaeeie
iieaeoeaie” (? Aea?ae?a?no?aoe?? 0197U006386), ? i?iaeo?a 3/127, 3.3/52
oa 4O/375-97, ui o?iainoaaeenue Oi?aae?iiyi ooiaeaiaioaeueieo
aeine?aeaeaiue I?iiaoee Oe?a?ie.

Iaoa ? caaea/? aeine?aeaeaiiy. Iniiaia iaoa ?iaioe iieyaaea o
anoaiiaeaii? ia iniia? nenoaiaoe/iiai aea/aiiy ?aaeien-aeanoeainoae
eii?aeeiaoe?eieo niieoe aca?iica’yceo i?ae aoaeiaith oao?aaiiaeueieo
eiiieaen?a iaoae?a c acioai?nieie e?aaiaeaie ? iniaeeainoyie
oa?iiaeeiai?/iiai oa e?iaoe/iiai aniaeo?a ?o ?aaeien-iiaaae?iee. sse
ia’?eoe aeine?aeaeaiiy aoee aea?ai? ?aaeien-ia?e M???/??L i?eaeth, i?ae?
oa eiaaeueoo, ui aeicaieyei oe?eani?yiiaaii aa??thaaoe aeaeo?iiio
eiio?ao?aoe?th oeaio?aeueiiai ?iia — 3d6 (Co???), 3d7 (Co??, Ni???), 3d8
(Ni??, Cu???), 3d9 (Cu??) ? aeaaaei iiaeeea?noue ii??aiyeueiiai aea/aiiy
aeanoeainoae ?ciaeaeo?iiieo ?ii?a ??cieo iaoae?a a ?aeaioe/iiio
e?aaiaeiiio ioi/aii?. A yeino? e?aaiae?a aoee aeei?enoai? iie?aeaioaoi?
acioai?ni? niieoee iae?ioeeee?/ii? ? a?aee?eoieaioethaiai? aoaeiae,
ine?eueee aiie iaaeaaaee oe?ie? iiaeeeaino? aeey no?oeoo?ieo aa??aoe?e ?
aeicaieyee aoaeoeaii noaa?e?coaaoe iaoaee a nooiai? ieeniaiiy +3. Aeey
?icoe?aiiy ani?oeiaioo e?aaiae?a ? iiooeo iiaeo oeyo?a oi?aae?iiy
?aaeien-aeanoeainoyie eiiieaen?a aoee ?ic?iaeai? iaoiaeeee neioaco iiaeo
iae?ioeeee?/ieo niieoe.

Iniiaio oaaao a ?iaio? aoei i?eae?eaii oaeei aniaeoai ?aaeien-iiaaae?iee
eii?aeeiaoe?eieo niieoe: 1) iiooeo iiaeo oeyo?a oa?iiaeeiai?/ii?
noaa?e?caoe?? i?eaeth oa i?ae? a iao?aaeeoe?eiiio nooiai? ieeniaiiy +3;
2) aeine?aeaeaiith e?iaoe/ii? noaa?e?caoe?? ?ii?a iaoae?a o aenieiio
nooiai? ieeniaiiy (niia?eueiaiiy aioo??oiueinoa?ieo ?aaeoe?e
a?aeiiaeaiiy i?eaeth(???) oa i?ae?(???) ca ?aooiie ieeniaiiy ai?iiiai
e?aaiaeo); 3) aea/aiith ?aaeoe?eii? caeaoiino? eiiieaen?a a
?aaeien-i?ioeanao, ui noi?iaiaeaeothoueny aiiie?oe/iei ?ic?eaii ca’yceo
iaoae-aen?aeueiee e?aaiae, oa c’ynoaaiiy aieeao ciai?oi?o /eiiee?a ia ?o
ia?aa?a (oa?ii- oa oioi?iaeoeiaai? ?aaeoe??); 4) anoaiiaeaiith
e?iaoe/ieo iniaeeainoae ia?aa?ao ?aaeoe?e ieeniaiiy oao?aaiiaeueieo
eiiieaen?a iaoae?a(II) iai?aai?/ieie ieenieeaie.

Iaoeiaa iiaecia io?eiaieo ?acoeueoao?a. ?ic?iaeai? i?ea?iaeuei?
iaoiaeeee oaiieaoiiai neioaco aeecueei 50 iiaeo niieoe i?eaeth(??) oa
i?ae?(??), aei yeeo a?aeiinyoueny: eiiieaene c oao?aaeaioaoieie iaioa- ?
aaenaacaiae?ioeeeeaie, ui i?noyoue iaeii?aeeiiaai? aoiie acioo oa
iaiaeaioi? ooieoe?iiaeuei? cai?nieee; eiiieaene c a?aee?eoieaioethaiaeie
oa 13- /e 14-/eaiieie iae?ioeeee?/ieie e?aaiaeaie, ui i?noyoue aea?
ai?ii? oa aea? ai?aei? aeiii?i? a?oie; a?n(iae?ioeeee?/i?) eiiieaene ia
iniia? 14-/eaiieo noaiaeeieoeue.

Anoaiiaeai? iniiai? oaeoi?e, ye? aecia/athoue aaee/eie
?aaeien-iioaioe?ae?a ia? NiIII/IIL ? CuIII/IIL a oao?aaiiaeueieo
eiiieaenao. Iieacaii, ui aaaeeeao ?ieue a oa?iiaeeiai?/i?e noaa?e?caoe??
aenieiai nooiaiy ieeniaiiy a?ae?a?athoue i?inoi?iaa aoaeiaa
aeaaoi??aeueieo e?aaiae?a oa ?o caeaoi?noue caaeiaieueiyoe noa?aio?i?/i?
aeiiae i?eaeth(???) oa i?ae?(???).

Anoaiiaeai? caaaeuei? caeiiii??iino? ia?aa?ao aioo??oiueinoa?ieo
?aaeien-?aaeoe?e a?aeiiaeaiiy iaoae?a(???) ca ?aooiie ieeniaiiy
aeaaoi??aeueiiai e?aaiaeo. Iieacaii, ui e?iaoe/ia noaa?euei?noue
i?eaeth(???) oa i?ae?(???) a oao?aaca ioi/aii? caaaeii ciaioo?oueny c?
ca?eueoaiiyi ?aaeien-iioaioe?aeo ia?e IIII/IIL, iaeiae ?nio? iecea
aeiaeaoeiaeo oaeoi??a, ye? aieeaathoue ia oaeaee?noue ?iceeaaeo
ieeniaieo oi?i eiiieaen?a.

C’yniaaiee aieea aoaeiae aeaaoi??aeueiiai e?aaiaeo a 5-eii?aeeiiaaieo
eiaaeueo(???)-aee?eueieo eiiieaenao ia e?iaoe/i? oa?aeoa?enoeee
aiiie?oe/iiai ?ic?eao aen?aeueiiai ca’yceo eiaaeueo-aoaeaoeue.
Anoaiiaeaiee aieea i?e?iaee aen?aeueiiai e?aaiaeo ia iniaeeaino?
ia?aa?ao ?aaeoe?e oioia?aeiiaeaiiy aeeaaeiaai?aeieo eiiieaen?a
eiaaeueoo(???) c oao?aaeaioaoieie iae?ioeeee?/ieie ai?iaie ? iieacaii,
ui aoaeoeai?noue aiiie?oe/iiai ?ic?eao ca’yceo eiaaeueo — aaeiaai?ae
aecia/a?oueny aeaeo?iiieie aeanoeainoyie aen?aeueieo e?aaiae?a oa
?aaeoe?eiith caeaoi?noth ?aaeeeae?a, ui ooai?ththoueny a ?acoeueoao?
ia?aiino aeaeo?iia.

Anoaiiaeai? e?iaoe/i? iniaeeaino? ?aaeoe?e oao?aaiiaeueieo eiiieaen?a
i?eaeth(??) ? i?ae?(??) c ieenieeaie ??cii? i?e?iaee. Iieacaii, ui
ieeniaiiy iae?ioeeee?/ieo eiiieaen?a i?eaeth(??) a?iiao-?iiaie a
caeaaeiino? a?ae aoaeiae e?aaiaeo a?aeaoaa?oueny aai iaeaoae?oe/iei
oeyoii, aai ? aaoieaoae?oe/iei. A oie aea /an, ieeniaiiy an?o eiiieaen?a
i?eaeth(??) ia?ieniaeenoeueoao-?iiaie a?aeaoaa?oueny ca iaeiaeiaei
o?i?/iei iaoai?ciii, i?e oeueiio i?e?iaea aeaiaioa?iiai aeoo ia?aiino
aeaeo?iia aecia/a?oueny i?inoi?iaith aoaeiaith eiiieaenii? niieoee ?
i?e?iaeith aeiii?ieo aoii?a e?aaiaeo. Ii??aiyeueia aeine?aeaeaiiy
?aaeoe?eii? caeaoiino? eiiieaen?a i?eaeth(??) oa i?ae?(??) c
a?aee?eoieaioethaiaeie ae?ienioao?aai?iaie a ?aaeoe?yo c
ia?ieniaeenoeueoaoii cana?ae/eei aioo??oiueinoa?iee i?ioean ieeniaiiy
eaaae?aoii-ieaia?ieo eiiieaen?a i?eaeth(??) oa ciai?oiueinoa?iee
iaoai?ci ieeniaiiy oanoeeii?aeeiiaaieo niieoe i?ae?(??).

A ?acoeueoao? aea/aiiy oa?iiaeeiai?/ieo ? e?iaoe/ieo oa?aeoa?enoee
?aaeoe?e ca o/anoth ?aaeien-ia? IIII/IIL aoa ciaeaeaiee iaa?aeiiee
?ai?oa i?ioean aaoieaoae?oe/iiai aiiie?co ca’yceo eiaaeueo-aoaeaoeue oa
i?iaeaiiino?iaaia o/anoue iae?ioeeee?/ieo eiiieaen?a i?eaeth(??,???) a
eieeaaeueieo o?i?/ieo ?aaeoe?yo c a?iiaoii.

I?aeoe/ia cia/aiiy io?eiaieo ?acoeueoao?a. Cai?iiiiiaai? niiniae
oe?eani?yiiaaiiai oi?aae?iiy aaee/eiaie ?aaeien-iioaioe?ae?a ia?
NiIII/IIL ? CuIII/IIL a oe?ieiio ae?aiacii? ?o cia/aiue oeyoii ci?ie
aoaeiae aeaaoi??aeueieo e?aaiae?a, i?e?iaee ?o aeiii?ieo aoii?a aai
neeaaeo na?aaeiaeua, a oaeiae niiniae io?eiaiiy e?iaoe/ii noaa?eueieo
eiiieaen?a, ui oa?aeoa?ecothoueny aenieeie aeiaeaoieie
?aaeien-iioaioe?aeaie.

I?iaeaiiino?iaai? iiaeeeaino? aeei?enoaiiy aeayeeo c aeine?aeaeaieo
niieoe a i?ioeanao, ui iiaeooue ciaeoe i?aeoe/ia canoinoaaiiy:

acaiae?ioeeee?/ieo eiiieaen?a eiaaeueoo ye eaoae?caoi??a
oioi?i?oe?eiaaiiai ieeniaiiy nie?o?a iieaeoey?iei eeniai;

oao?aacaaioeaiiaeo eiiieaen?a eiaaeueoo ye eaoae?caoi??a ia?aaea/?
eaioethaa c iie?ia?o ia iiiiia? a ?aaeeeaeuei?e iie?ia?ecaoe?? ae?eeiaeo
iiiiia??a;

eii?aeeiaoe?eieo niieoe i?eaeth(??,???) c iae?ioeeee?/ieie oa
a?aee?eoieaioethaiaeie e?aaiaeaie ye ?ia?a?oi??a i?ioean?a
?aaeeeaeueiiai ieeniaiiy i?aai?/ieo niieoe eeniai.

Iniaenoee aianie caeiaoaa/a. Oi?ioethaaiiy iaoeiaiai iai?yieo,
iaa?oiooaaiiy ?aea?, iinoaiiaea caaea/, aea?? ia’?eo?a aeine?aeaeaiiy,
?ioa?i?aoaoe?y oa ocaaaeueiaiiy ?acoeueoao?a neeaaea? iniaenoee aianie
caeiaoaa/a. Aenia?eiaioaeuei? aeai? aoee io?eiai? ni?eueii c N.A.
?inioith, TH.?.Eiaaeaiei, N.I.Aaa?eoai, ?.I.Iaeiooaiii, iaoeiaei
ea??aieeii /e?o aeena?oaoe?eieo ?ia?o aoa caeiaoaa/. A aeine?aeaeaii?
eieeaaeueieo o?i?/ieo ?aaeoe?e i?eeiaee o/anoue ae.o.i. E.I.Oeoiiiaa oa
e.o.i. E.I.Cae?aanueea, aea/aiiy eaoae?oe/ieo aeanoeainoae eiiieaen?a a
i?ioeanao ?aaeeeaeueii? iie?ia?ecaoe?? i?iaiaeeeinue ni?eueii c e.o.i.
A.A.A??aei?aei, aeine?aeaeaiiy ?ia?aoth/eo aeanoeainoae eiiieaen?a
i?eaeth aeeiioaaeinue ni?eueii c /e.-ei?. IAI Oe?a?ie A.I.Eiaooiii oa
e.o.i. I.?.Eocueiaiei. A aeine?aeaeaii? oioio?i?/ieo aeanoeainoae
aeayeeo eiiieaen?a eiaaeueoo(???) i?eeiaea o/anoue e.o.i. A.A.E?aniiaa.

Aaoi? aeneiaeth? ue?o aaey/i?noue iaoeiaiio eiinoeueoaioia? aeaaeai?eo
IAI Oe?a?ie E.A.ssoeeie?nueeiio, aac anaa?/ii? i?aeo?eiee oa
iaaecae/aeii ei?enieo ii?aae yeiai aeeiiaiiy ?iaioe aoei a iaiiaeeeaei.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iaoa??aee aeena?oaoe??
aeiiia?aeaeenue ia eiioa?aioe?yo: XOIII, OOIV, OOV???, OOO International
Conference on Coordination Chemistry (Boulder, USA, 1984; Athens,
Greece, 1986; Gera, DDR, 1990; Kyoto, Japan, 1994), O???, OV, OV??, O?O,
OO, OO?? International Symposium on Macrocyclic Chemistry (Hamburg, BRD,
1983, Odessa, USSR, 1990; Provo, USA, 1992; Lawrance, USA,1994;
Jerusalem, Israel, 1995; Seoul, South Korea, 1997), O?? IUPAC Conference
on Chemical Thermodynamics (Provo, USA, 1992), VI, VII Jenaer
Mikrosymposium fur Koordination- und Elementorganische Chemie (Eisenach,
DDR, 1985, 1987), OV Conference on Coordination Chemistry (Smolenice,
Slovakia, 1995), O?V Iaiaeaeaaaneii nuacaea ii iauae e i?eeeaaeiie oeiee
(Oaoeaio, 1989), O??? — OV?? Ananithciuo *oaaaaneeo niaauaieyo ii oeiee
eiiieaeniuo niaaeeiaiee (Iineaa, 1978; Eaaiiai, 1981; Eeaa, 1985;
E?aniiy?ne, 1987; Ieine, 1990), ?, ??? — V Ananithciuo eiioa?aioeeyo ii
eii?aeeiaoeeiiiie e oece/aneie oeiee ii?oe?eiia (Eaaiiai, 1979, 1988;
Naia?eaiae, 1982; A?aaai, 1984), ??, ??? Ananithciuo eiioa?aioeeyo ii
oeiee e aeioeiee iae?ioeeeee/aneeo niaaeeiaiee (Iaeanna, 1984; Eaaiiai,
1988), VII, V???, O Ananithciuo niaauaieyo “Oece/aneea e iaoaiaoe/aneea
iaoiaeu a eii?aeeiaoeeiiiie oeiee” (Eeoeiaa, 1980; 1983; 1990), IV
Ananithciie eiioa?aioeee ii iaoaeeii?aaie/aneie oeiee (Eacaiue, 1988),
IV Ananithciii niaauaiee ii oioioeiee (Iiaine-ae?ne, 1989), O, O?, O??,
O???, O?V ?anioae?eainueeeo eiioa?aioe?yo c iai?aai?/ii? o?i??
(N?ioa?iiieue, 1981, 1989; Oaeai?iae, 1986, 1992; Ee?a, 1996),
Eiioa?aioe?yo-eiieo?nao ?inoeoooo o?ce/ii? o?i?? ?i.E.A.Iena?aeaanueeiai
IAI Oe?a?ie (1989, 1991, 1992, 1996).

Ioae?eaoe??. Iniiaiee ci?no ?iaioe aeeeaaeaiee a iiiia?ao??, 2
aaoi?nueeeo na?aeioeoaao N?N? ? 53 iaoeiaeo noaooyo.

No?oeoo?a oa ia’?i aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny c anooio,
naie ?icae?e?a, iniiaieo i?aenoie?a, aeniiae?a oa nieneo oeeoiaaieo
e?oa?aoo?ieo aeaea?ae (461 iaeiaioaaiiy). ?iaioa aeeeaaeaia ia 336 noi?.
? i?noeoue 70 ?enoie?a, 17 noai oa 58 oaaeeoeue.

Ia?oa /anoeia aeena?oaoe?? (?icae?ee 1 ? 2) i?enay/aia ?icaeyaeo
oa?iiaeeiai?/iiai aniaeoo noaa?e?caoe?? eiiieaen?a i?eaeth(???) oa
i?ae?(???). A ae?oa?e /anoei? (?icae?ee 3 ? 4) ?icaeyioo? e?iaoe/i?
iniaeeaino? oa iaoai?cie aioo??oiueinoa?ieo ?aaeien-i?ioean?a ca o/anoth
eiiieaen?a iaoae?a(???). A o?ao?e /anoei? (?icae?ee 5 oa 6) aeeeaaeai?
?acoeueoaoe aea/aiiy e?iaoe/ieo iniaeeainoae ?aaeoe?e ieeniaiiy
eiiieaen?a i?eaeth(??) oa i?ae?(??) c oao?aaca e?aaiaeaie iai?aai?/ieie
ieenieeaie ??cii? i?e?iaee. A ?icae?e? 7 iienai? ?ic?iaeai? a ?iaio?
oeyoe neioaco iiaeo eii?aeeiaoe?eieo niieoe oa aeei?enoai?
aenia?eiaioaeuei? iaoiaee. Aoaeiaa iaea?eueo aaaeeeaeo e?aaiae?a
iieacaia ia ?en.1.

Iniiaiee ci?no aeena?oaoe??

Aeine?aeaeaiiy aieeao aoaeiae acioai?nieo e?aaiae?a ia
ieenithaaeueii-a?aeiiaethaaeuei? iioaioe?aee ia? IIII/IIL (I = Ni oa Cu)

1.1. ?aaeien-iioaioe?aee ia?e NiIII/IIL a oao?aaca ? aaenaaca ioi/aii?,
noi?iiaaiiio ca o/anoth a?aee?eoieaioethaiaeo ai?iieo e?aaiae?a

C aiae?co e?oa?aoo?ieo aeaieo (?icae?e 1) aeieeaaea iaiao?aei?noue
c’ynoaaiiy ieoaiiy, /e ? iae?ioeeee?/ia i?e?iaea e?aaiae?a i?eioeeiiaith
aeey oa?iiaeeiai?/ii? oa e?iaoe/ii? noaa?e?caoe?? i?eaeth(???). Aeey
oeueiai iaoiaeii oeeee?/ii? aieueoaiia?iiao??? aoee aeine?aeaeai?
eiiieaene i?eaeth c a?aee?eoieaioethaiaeie oao?aai?iaie 2,2,2-tet
(1,4,7,10-oao?aaca-aeaeai), 2,3,2-tet (1,4,8,11-oao?aacaoiaeaeai) oa
3,2,3-tet (1,5,8,12-oao?aacaaeiaeaeai) ? i?iaaaeaia ii??aiyiiy ?o
oi?iaeueieo ?aaeien-iioaioe?ae?a Af c iioaioe?aeaie eiiieaeno oeeeeaio
NiL1 (oaae. 1, yeui ia a?aei?/aii niaoe?aeueii, ooo ? a iiaeaeueoiio an?
aaee/eie Af aoee io?eiai? i?e oaeaeeino? ?icai?oee iioaioe?aeo v=50 iA/n
? oaiia?aoo?? 293 E ia ?iai/iio neeiaoaeaoeaaiio aeaeo?iae? ? i?eaaaeai?
a?aei. IEA; ye oa?aeoa?enoeea iai?ioiino? i?ioean?a a aeoaeeao iaaaaeaia
a?aenoaiue a iA i?ae aiiaeiei oa eaoiaeiei i?eaie).

Oaaeeoey 1. ?aaeien-iioaioe?aee ia?e NiIII/IIL (iA) oa
eiinoaioe oaeaeeino? ?iceeaaeo a) (n-1) eiiieaen?a i?eaeth(???) c
oao?aai?iaie L a ??cieo na?aaeiaeuao

E?aaiae L 0,1 iieue/e NaClO4 0,1 iieue/e Na2SO4 0,5 iieue/e Na2SO4

2,2,2-tet 980 (250)a) 815 (105) 795 (95)

2,3,2-tet 830 (85); k?icee = 1,5(10-4 660 (80); k?icee = 1,4(10-5 630
(65)

3,2,3,-tet 840 (75) 660 (65) 640 (60)

L1 750 (65); k?icee = 3,0(10-5 510 (65); k?icee < 10-6 490 (65) I?ei?oee: a) a?aeiia?aeii a 0,1 I IClO4 oa 0,1 I I2SO4; a) i?e v=500 iA/n. ?en.1. No?oeoo?i? oi?ioee aeayeeo acioai?nieo e?aaiae?a Oa?aeoa?enoeee aieueoaiia?ia?ai aeicaieythoue o?aeooaaoe aeaeo?io?i?/io iiaaae?ieo an?o niieoe, ca aeiyoeii Ni(2,2,2-tet) a ia?oei?aoiiio na?aaeiaeu?, ye eaac?iai?ioio. sse aeaeii, i?ae eiiieaenaie a?aee?eoieaioethaiaeo ai?i?a ? iae?ioeeeeo a?aenooi? i?eioeeiia? a?aei?iiino?, oi/a ?aaeien-iioaioe?aee ia?e NiIII/IIL eiiieaen?a c 2,3,2,-tet i 3,2,3-tet aeaui aeu?, i?ae iioaioe?aee NiIII/IIL1. Iayai?noue o ?ic/eiao noeueoao- aai oinoao-?ii?a (Af ia? NiIII\IIL a oinoaoiiio aooa?? i?e ?I 6,86 aei??aith? 610 (95) oa 480 (85) iA aeey L=2,3,2-tet ? L1 a?aeiia?aeii) i?eaiaeeoue aei oa?iiaeeiai?/ii? noaa?e?caoe?? aeuiai nooiaiy ieeniaiiy aiane?aeie aen?aeueii? eii?aeeiaoe?? ieniai?ii?a aei i?eaeth(???). C?iaeaiee aeniiaie noino?oueny eiiieaen?a c ieiueiiei NiN4-o?iiioi?ii. Aeey c’ynoaaiiy ieoaiiy, /e caeaoi? noaa?e?coaaoe i?eaeue(III) iaoeeee?/i? a?- ? o?eaeaioaoi? ai?ie, ui oi?iothoue ieoaaae?e/iee NiN6-o?iiioi?, aoee i?iaiae?ciaai? aaee/eie Af ia?e NiIII/II(N6), io?eiai? iaie aeey eiiieaen?a 7, 8 ? 9, oa iayai? a e?oa?aoo?? aeey ?ioeo niieoe (?en.2). Ia aeeaey/enue ia iiae?aio aoaeiao eiiieaen?a, ae?aiacii ci?ie ?o ?aaeien-iioaioe?ae?a neeaaea? 200 iA. Iiaeia i?eionoeoe, ui aaee/eie Af aeey ieo ca’ycai? c aia?a?yie, ye? iaiao?aei? aeey ia?aaoaeiae eii?aeeiaoe?eieo iie?aae??a i?e ci?i? nooiaiy ieeniaiiy iaoaeo, oiaoi aecia/athoueny aieiaiei /eiii eiioi?iaoe?eiith aio/e?noth e?aaiae?a, oiae? ye nooi?iue aee?eoaaiiy aeiii?ieo aoii?a a?a? iaioo ?ieue. ?en. 2. Aoaeiaa oa oa?aeoa?enoeee eiiieaen?a c NiN6-o?iiioi?ii (aiaei? ?ic/eie, 0,1 I NaClO4, 10Dq a 103 ni-1). A?aoiaoth/e, ui niaeo?io?i?/iee ia?aiao? 10Dq eiiieaen?a c iaeiioeiiei e?aaiaeiei ioi/aiiyi iiaea ?icaeyaeaoenue ye oaeee, ui oa?aeoa?eco? aoaeoeai?noue ia?ae?eaaiiy i?a?oaeae iaoaeo oa e?aaiaeo, ?ioeie neiaaie, noa?e/io "iai?oaeai?noue" o?iiioi?o, aoa i?iaiae?ciaaiee ca’ycie i?ae aaee/eiaie Af ? Dq eiiieaen?a i?eaeth(II) (?en.3). A?i aeyaeany aeecueeei aei e?i?eiiai (eiao?oe??io ei?aeyoe?? r=0,85). C io?eiaii? ei?aeyoe?? aeieeaa?, ui aoaeoeai?noue oa?iiaeeiai?/ii? noaa?e?caoe?? i?eaeth(???) i?iii?oe?eia nee? iiey ai?iiiai e?aaiaeo. Iaiao?aeii a?aei?oeoe a?aeoeeaiiy a?ae e?i?eii? caeaaeiino? oi/ee 9, yea a?aeiia?aea? ?aeei?e niieooe?, "aa?oeio" e?aaiaeo yei? ooai?th? iaeii?aeeiiaaiee aoii acioo. A??ia?aeii, aeaeo?iii? oa?aeoa?enoeee aeaiiai aoiia ? ia?aiao?e ca'yce?a N-C a?ae??ciythoueny a?ae oaeeo aeey aoiia aoaeaoeth ? N-N ca'yce?a, ui ? i?eaiaeeoue aei a?aei?iieo (iai?., a?ae 3) aia?aaoe/ieo cao?ao ia eiioi?iaoe?ei? ci?ie, ye? noi?iaiaeaeothoue ieeniaiiy i?eaeth(II). Aiaeia?/ia ea?oeia niinoa??aaeanue ? i?e ii??aiyii? ?aaeien-aeanoeainoae oao?aaiiaeueieo eiiieaen?a c oeeeeaiii oa acaoeeeeaiaie (aeea. ieae/a). ?en. 3. Ei?aeyoe?y i?ae aaee/eiaie Af oa 10Dq aeey eiiieaen?a i?eaeth c aaenaaca o?iiioi?ii (oeeo?e a?aeiia?aeathoue iiia?ai eiiieaen?a ia ?en. 2) Io?eiai? ?acoeueoaoe aeicaieythoue c?iaeoe aeniiaie, ui oeeee?/ia i?e?iaea e?aaiaeo ia ? iniiaiei oaeoi?ii aeey oa?iiaeeiai?/i?e noaa?e?caoe?? i?eaeth(III) a ai?iiiio ioi/aii?. A ?iaio? cai?iiiiiaaiee i?aeo?ae, yeee aeicaiey? io?eiaoe iaai? e?euee?ni? oa?aeoa?enoeee aieeao aoaeiae e?aaiaeo ia aeanoeaino? eiiieaen?a i?eaeth(??,???). Aeey oeueiai aeoiaey/e c ??aiyiiy Ia?inoa aoa io?eiaiee ae?ac lg ((III) = lg ((II) - (Af / 0,059 (1) aea aaee/eie ((II)=E(MIILnioe)/E(MIILnae) oa ((?II)=E(MIIILnioe)/E(MIIILnae) oa?aeoa?ecothoue a?aeiioaiiy oa?iiaeeiai?/ieo eiinoaio no?eeino? eiiieaen?a c iae?ioeeee?/iei (“ioe”) ? a?aee?eoieaioethaiaeie (“ae”) e?aaiaeaie, a (Af = Afioe - Afae. Aaniethoi? cia/aiiy aaee/ei MIIILn iaa?aeii?, iaeiae ??ai. (1) aeicaiey? ?ic?aooaaoe ?o a?aeiioaiiy ((?II). Aeiaaeie, eiee ((II) > ((III) (oiaoi,
(Ef ( 0 ?, a?aeiia?aeii, ((G0 ( 0), na?ae/eoue i?i oa?iiaeeiai?/io
aeanoaa?e?caoe?th i?eaeth(???) a iae?ioeeee?/iiio eiiieaen?, ? iaaiaee,
((II) < ((III) icia/a?, ui iae?ioeeee?/iee e?aaiae aoaeoeai?oa noaa?e?co? i?eaeue(???), i?ae a?aee?eoieaioethaiaee ai?i. sse aeo?ea? c ?ic?aooie?a, iaeieae/ee ?aaeien-iioaioe?ae eiiieaeno NiL1 iaoiiaeaiee oei, ui 14-/eaiiee e?aaiae ooai?th? iaea?eueo oa?iiaeeiai?/ii no?eeee eiiieaen c i?eaeai(???). Iaeiae a?aei?iiino? i?ae iei ? iaoeeee?/ieie ai?iaie 2,3,2-tet oa 3,2,3-tet ? aeineoue iacia/ieie. Oea na?ae/eoue, ui aeai? oao?aai?ie caaaeyee nai?e eiioi?iaoe?ei?e aio/eino? caaeiaieueiythoue noa?aio?i?/i? aeiiae i?eaeth(???) aac noa?e/ieo iai?oa. Ii??aiyiiy ae aaee/ei ( aeey eiiieaen?a 13- ? 15-/eaiieo iae?ioeeee?a c iaeiiai aieo, oa 2,3,2-tet ? 3,2,3-tet c ?ioiai, aeicaiey? noaa?aeaeoaaoe, ui aeanoaa?e?caoe?y aenieiai nooiaiy ieeniaiiy a aeaieo iae?ioeeee?/ieo eiiieaenao aeeeeeaia iaioith oa?iiaeeiai?/iith no?ee?noth eiiieaen?a i?eaeth(???) 1.2. ?aaeien-aeanoeaino? eiiieaen?a i?eaeth oa i?ae? c acaoeeeeaiiaeie e?aaiaeaie C iaoith iiooeo iiaeo i?aeoiae?a aei ea?oaaiiy ?aaeien-aeanoeainoyie ia? I???/??L oeyoii ci?ie no?oeoo?ieo ia?aiao??a iae?ioeeee?a iaie aoee neioaciaai? iia? eiiieaene i?eaeth oa i?ae? c e?aaiaeaie aca- oa ae?acaoeeeeaiiaiai oei?a L2-L12, L16-L18 (aeea. ?en.1), a e?noyeao yeeo iayai? iaeii?aeeiiaai? (aeenoaeuei?) aoiie acioo Naeeno. Aeine?aeaeaiiy aeaeo?io?i?/ii? iiaaae?iee eiiieaen?a i?eaeth cana?ae/eei (oaae. 2), ui Af ia?e Ni???/??L noa? iaio iiceoeaiei i?e ia?aoiae? a?ae aoeaoii?o?eeo (ACN) aei iaeo?aeueieo aiaeieo ?ic/ei?a, a a inoaii?o ciaioo?oueny a ?yaeo aeaeo?ie?o?a NaClO4 SYMBOL 62 \f "Symbol" Na2SO4. Oea a?aeaeca?eaeth? aoaeo oa?iiaeeiai?/ii? noaa?e?caoe?? i?eaeth(???) aen?aeueieie e?aaiaeaie ACN ( H2O ( SO42-. Ca?eueoaiiy e?eueeino? Naeeno a e?aaiae? i?eaiaeeoue aei i?aeaeuaiiy Af. Aeey iiyniaiiy oeueiai aoaeoo iiaeooue aooe caeo/ai? o? ae a?aoiaioe, ui iaaaaeai? aeua aeey iiyniaiiy iiaaae?iee eiiieaen?a c NiN6-o?iiioi?ii. ?io? no?oeoo?i? ia?aiao?e e?aaiae?a (i?e?iaea Naeeno, iayai?noue iaiaeaioieo aeiii?ieo a?oi, a?n(iae?ioeeee?/ia) aoaeiaa e?aaiaeo) i?aeoe/ii ia aieeaathoue ia aaee/eie Af ia?e Ni???/??L. Oea na?ae/eoue i?i oa, ui ooieoe?iiaeuei? a?oie cai?niee?a ia eii?aeeiothoueny aei ?iia i?eaeth a iaio nooiaiyo ieeniaiiy, a oaeiae i?i a?aenooi?noue aeaeo?inoaoe/ii? aca?iiae?? i?ae ?iiaie i?eaeth a a?n(iae?ioeeee?/ieo) niieoeao. ?aaeien-iioaioe?aee Ni???/??L a eiiieaenao e?aaiae?a c ae?acaa?oeeeeiiiiaiiaei o?aaiaioii L15-L18 aeu? (Af (960 oa (1250 iA a n??/aiieeneeo ?ic/eiao), i?ae aeey eiiieaen?a 14-/eaiieo e?aaiae?a. Oea aeeeeeaia oei, ui ?o ii?iaeieia caiaea aeey i?eaeth(???). I?iya aeaio ?aaeien-i?ioean?a a oeeo niieoeao ca’ycaiee ia c ?o a?yaea?i?noth, ine?eueee niinoa??aa?oueny ? aeey NiL15, a iiynith?oueny i?enooi?noth o ?ic/ei? aeaio eiioi?ia??a. A oe?eiio aiaeia?/i? eiiieaenai i?eaeth oaiaeaioe?? oa?aeoa?i? ? aeey ia?e CuIII/IIL a ACN, oi/a a oeueiio aeiaaeeo aeey a?yaea?ii? niieoee c iaeei?iooei i?noeii Cu2L19 niinoa??aathoueny aeaa eaac?iai?ioi? i?ioeane ye iane?aeie aeaeo?inoaoe/ii? aca?iiae?? iaoae-iaoae (oaea aca?iiae?y i?iyaey?oueny ? a AI? niaeo?? aeaiiai eiiieaeno). Ii??aiyiiy io?eiaieo a neeueiieeneeo ?ic/eiao aaee/ei Af eiiieaen?a i?eaeth oa i?ae? na?ae/eoue, ui i?e ?ioeo aiaeia?/ieo oiiaao ia?o? oa?aeoa?ecothoueny ieae/eie ?aaeien-iioaioe?aeaie. I?e oeueiio a caeaaeiino? a?ae i?e?iaee cai?nieea i?e Naeeno ia? i?noea aai aeoaea nooo?aa (aei 300 iA, eiiieaene c L2-L5, L8), aai cia/ii iaioa (aei 100 iA, eiiieaene c L6, L7) i?aeaeuaiiy Af ii??aiyii c ML1. Oaea iiaaae?iea iiynith?oueny i?ioiioaaiiyi a ia?oiio aeiaaeeo Naeeno, ? ca’ycaiith c oeei aeaeo?inoaoe/iith aeanoaa?e?caoe??th I(???). I?e iayaiino? a eiiieaenao iaiaeaioii? Oaaeeoey 2. ?aaeien-iioaioe?aee ia? I???/??L (iA) eiiieaen?a i?eaeth ? i?ae? c acaoeeeeaiaie ? ?o iio?aeieie E?aaiae Eiiieaene i?eaeth Eiiieaene i?ae? L ACN H2O ACN H2O 0,1 I OAAI 0,1 I NaClO4 0,5 I Na2SO4 9,5 I HClO4 0,02 I OAAI 9,5 I HClO4 L1 990 (75) 740 (70) 495(70) 640 (80) - 760 (60) L2 1020 (90) 780 (80) 520 (65) 890 (60) - - L3 1000 (60) 790 (75) 530 (65) 910 (60) 1500 (90) 1130a) L4 - 800 (75) 520 (70) - - 1060 (120) L5 - 825 (90) 515 (70) 730 (90) - 1180a) L6 - 820 (80) 510 (75) 740 (70) - 880 (85) L7 - 815 (110) 515 (80) 730 (85) - 875 (70) L8 - 830 (75) 540 (70) - - - L9 1010 (70) 800 (100) 510 (100) - 1450 (100) 1540 (100) 830 (110) 1130a) L10,L12 990 (65) 790 (100) 500 (100) - 1510 (100) (1700 L13 - - - - - 850 (80) I?ei?oea: a) iaiai?ioiee i?ioean, i?eaaaeaia cia/aiiy aiiaeiiai i?ea. N(Me)2-a?oie naia aiia i?ioiio?oueny a ia?oo /a?ao, ? oea ni?e/eiy? iaioee aieea ia iaoae(???), ine?eueee oey a?oia ciaoiaeeoueny ia a?eueo?e a?aenoai? a?ae iueiai. Aeey eiiieaen?a i?eaeth c e?aaiaeaie L2, L3 ? L8 ?nio? ?ioa iiaeeea?noue oi?aae?iiy ?aaeien-aeanoeainoyie. Iaie aoei anoaiiaeaii, ui aeey oeeo niieoe iieiaeaiiy ??aiiaaae i?ae 4- oa 6-eii?aeeiiaaieie oi?iaie a n??/aiieeneeo ?ic/eiao caeaaeeoue a?ae ?I aiane?aeie aeaiooeaio?iaiai ca'ycoaaiiy a?ae?inoeueoao-ai?ii?a oeyoii ooai?aiiy eii?aeeiaoe?eiiai (Ni??-OSO3H) ? aiaeiaaiai (Naeeno...HOSO3-) ca'yce?a. Ia a?aei?io a?ae oei?iieeneeo na?aaeiaeu aaee/eie Af oeeo niieoe oaeiae caeaaeaoue a?ae ?I a n??/aiieeneeo ?ic/eiao (?en.4). I?e ?I (3, eiee noeueoao ciaoiaeeoueny o ?ic/ei? a oi?i? SO42-, iaaaaeai? ia ?en.4 caeaaeiino? iiyniththoueny aoaeoeai?oith noaa?e?caoe??th i?eaeth(???) a noeueoaoieo eiiieaenao [NiL(SO4)2]- ii??aiyii c [NiL(H2O)2]3+, i?enooi?ie a oei?iieeneeo ?ic/eiao A a?eueo eeneeo ?ic/eiao ia iiaeia iaoooaaoe i? ooai?aiiyi eiiieaenaie NiIIL3 oa NiIIL8 6-eii?aeeiiaaieo a?ae?inoeueoaoieo aaeoeo?a, i? ciaioaiiyi noaa?e?caoe?? i?eaeth(???) e?aaiaeaie SO4H- ii??aiyii c SO42- (inoaii?e aoaeo a /enoiio aeaeyae? i?iyaey? naaa o aeiaaeeo NiL1), iaeiae caaaeii neiaaoi?noue ci?i Af ? iieiaeaiiy ??aiiaa- ?en. 4. Caeaaei?noue Af ia?e Ni???/??L a?ae ?I a aiaeieo ?ic/eiao, ui i?noyoue 0,5 I NaClO4 (ca?oe? cia/ee), /e 0,2 I Na2SO4 (oaii? cia/ee); L=L1 ((), L3 ((), L8 ((). ae i?ae 4- oa 6-eii?aeeiiaaieie oi?iaie eiiieaen?a neoaeeoue i?aeoaa?aeaeaiiyi a?eueo oo?oaeiaiiai (( ia 50 iA) ieeniaiiy inoaii?o. 1.3. Aieea eiioi?iaoe?? iae?ioeeeeo oa i?e?iaee aeiii?ieo aoii?a ia ?aaeien-iioaioe?aee ia?e NiIII/IIL a eiiieaenao iaoeecai?uaieo e?aaiae?a C iaoith anoaiiaeaiiy aieeao o?i?/ii? aoaeiae oa eiioi?iaoe?? e?aaiae?a ia ?aaeien-iioaioe?aee niieoe i?eaeth aoea aei??yi? aaee/eie Af eiiieaen?a iaoeecai?uaieo e?aaiae?a L19-L29 (aeea. ?en.1, N-eiioi?ia?e iicia/ai? a?aoeueeeie aoeaaie). Oaaeeoey 3. ?aaeien-iioaioe?aee ia?e Ni???/??L N- oa N-eiioi?ia??a iaoeecai?uaieo iae?ioeeee?/ieo eiiieaen?a a 0,1 I H2SO4 E?aaiae L Af, iA E?aaiae L Af, iA E?aaiae L Af, iA L1 535 (60) SYMBOL 101 \f "Symbol" -L21 740 (65) L25 720 ( SYMBOL 163 \f "Symbol" 60) L19 555 (60) SYMBOL 98 \f "Symbol" -L22 705 (60), 865 (60) L26 790 (115) L20 695 (60),865 (60) SYMBOL 97 \f "Symbol" -L23 835 (160) SYMBOL 97 \f "Symbol" -L27 965 (100) SYMBOL 97 \f "Symbol" -L21 830 (145) SYMBOL 98 \f "Symbol" -L23 iaiai?. SYMBOL 98 \f "Symbol" -L27 950 (90) SYMBOL 98 \f "Symbol" -L21 iaiai?. SYMBOL 103 \f "Symbol" -L23 755 (70) L28 iaiai?. SYMBOL 103 \f "Symbol" -L21 745 (60) SYMBOL 98 \f "Symbol" -L24 745 (70) L29 1080 (80) sse aeaeii, aaaaeaiiy a 6-/eaii? oaeaoi? oeeeee aen?aeueieo cai?niee?a (Iaaen) i?eaiaeeoue aei i?aeaeuaiiy Af - an? aaenaiaoeeuei? iio?aei? oa?aeoa?ecothoueny a?eueo iiceoeaieie iioaioe?aeaie, i?ae NiL1, oiae? ye Af aeey NiL19, aea iaeaeaa cai?nieee aeaaoi??aeuei?, i?aeoe/ii ia a?ae??ciythoueny a?ae NiL1 (aeai? noiniaii i?inoi?iai? aoaeiae niieoe acyo? c e?oa?aoo?e). Ca?eueoaiiy iaiane/aiino? e?aaiaeo i?eaiaeeoue aei aeanoaa?e?caoe?? i?eaeth(???), i?e oeueiio a?eueo iiceoeaia cia/aiiy Af aeey iiii?iiaiai eiiieaeno NiL24 ii??aiyii c ae??iiaei NiL25 iiynith?oueny, a??ia?aeii, aeanoaa?e?coth/ei aoaeoii Iaaen a ia?o?e niieooe?. I?e/eiith aeanoaa?e?coth/iai aieeao aen?aeueieo cai?niee?a ? aeo?aoe aia?a?? ia eiioi?iaoe?ei? ci?ie a e?aaiae?, ye? iaiao?aei? aeey eii?aeeiaoe?? noeueoao-?ii?a aei i?eaeth(???). Iayai?noue Iaaen i?e aneiao?e/iiio aoii? ia i?eaiaeeoue aei i?aeaeuaiiy Af, ine?eueee a oaeeo eiiieaenao aaea iayaiee aen?aeueiee cai?niee a eiaei?e c aai-aeeiaoeeueieo a?oi. Iiaeia noaa?aeaeoaaoe, ui ia ?nio? ei?aeyoe?? i?ae noa?e/iith iai?oaeai?noth e?aaiaeo a Ni??L ? aaee/eiith Af ia?e Ni???/??L. Oae, eiiieaene e?aaiae?a c iaea?eueo noaa?eueieie eiioi?iaoe?yie oaeaoieo oeeee?a (L20, L22) ae?enii oa?aeoa?ecothoueny iaeieae/eie iioaioe?aeaie, iaeiae ?aaeien-iioaioe?ae iaea?eueo iai?oaeaiiai eiiieaeno SYMBOL 101 \f "Symbol" -NiL21 cian?i ia ? iaeaeuei. A eiiieaenao SYMBOL 97 \f "Symbol" -NiL21 ? SYMBOL 97 \f "Symbol" -NiL23, aea aeaa 6-/eaii? oaeaoi? oeeeee iathoue aeaoi?iiaaio eiioi?iaoe?th, niinoa??aa?oueny i?aeaeuaiiy Af ia (100 iA ii??aiyii c eiiieaenaie e?aaiae?a L20 /e L22. Aeey eiiieaen?a c aeaoi?iiaaieie 5-/eaiieie oeeeeaie ( SYMBOL 98 \f "Symbol" -NiL21, SYMBOL 98 \f "Symbol" -NiL23) oa?aeoa?i? iaiai?ioi? aeaeo?io?i?/i? i?ioeane. 1.4. ?aaeien-iioaioe?aee eiiieaen?a i?eaeth oa i?ae? c ai?aeai?nieie oao?aaca e?aaiaeaie a?aee?eoieaioethaiai? oa iae?ioeeee?/ii? aoaeiae Aeine?aeaeaiiy ?aaeien-aeanoeainoae eiiieaen?a i?eaeth oa i?ae? c e?aaiaeaie L30-L45 (aeea. ?en.1) aeicaieeei i?iaiae?coaaoe, ye ia noaa?e?caoe?th iaoae?a(???) aieeaa? iayai?noue a e?aaiaeao ai?aeieo a?oi oa aa??thaaiiy ?ici???a ? aca?iiiai ?icoaooaaiiy oaeaoieo oeeee?a a eiiieaenao. E??i aeaeo?io?i?/ieo aei??thaaiue (oaae.4), aeey aeine?aeaeaiiy aeaieo eiiieaen?a aoee aeei?enoai? iaoiaee ANI (MIIL, MIIIL) AI? (CuIIL, NiIIIL), 1I ? 13N ssI? (NiIIL). Oaaeeoey 4. Aia?a?? d-d ia?aoiae?a (a 103 ni-1, SYMBOL 101 \f "Symbol" a I-1 ni-1) i?ae?(??) ? i?eaeth(??) oa ?aaeien-iioaioe?aee ia? I???/??L (iA) a eiiieaenao ai?aeai?nieo e?aaiae?a E?aaiae Eiiieaene i?ae? Eiiieaene i?eaeth SYMBOL 110 \f "Symbol" iaen ( SYMBOL 101 \f "Symbol" ) Af a 0,1 I NaClO4 SYMBOL 110 \f "Symbol" eaen ( SYMBOL 101 \f "Symbol" ) Af a 0,1 I NaClO4 Af a 0,5 I Na2SO4 H2L30 19.1 (174) 595 (80) 24,0 (205) 620 (90) 585 (65) H2L31 18.9 (152) 490 (80) 24,0 (190) 550 (80) 495 (60) H2L32 19.3 (60) 755 (80) 22.1 (67) 645 (130) 615 (80) H2L33 19.1 (62) 740 (80) 22.0 (72) 645 (90) 605 (65) H2L34 18.5 (96) 805 (130) 21,2 (103) - 585 (160) H2L35 18.4 (65) 760 (135) 21,9 (66) 555 (100) 510 (65) H2L37 19,2 (100) 600 (100) 24,0 (79) 790 (150) 750(100) H2L38 19,4 (84) 600 (120) 23,8 (60) - - H2L39 19,8 (91) 680 (75) 21,7 (74) 580 (90) 545 (70) H2L40 20,2 (64) 680 (90) 21,9 (66) - - H2L41 19,7 (75) 730 (80) 21,4 (68) 625 (180) 595 (155) H2L42 19,6 (86) 820 (100) - - - H2L43 - - 25,3 (179) 580 (95) 545 (65) H4L44 18,0 (150) 560 i 660 23,2 (64) 750 (160) - H4L45 18.7 (66) 755 (60) 21,6 (93) 580(75);730(75) - sse aeaeii, ae?aiacii ci?i Ef ia?e Nu???/??L a eiiieaenao c iaoeeee?/ieie ai?aeaie aeinyaa? 300 iA, i?e/iio c? ca?eueoaiiyi e?eueeino? 6-/eaiieo oaeaoieo oeeee?a aaee/eie Ef a ?yaeo CuL30-CuL35 noathoue a?eueo iiceoeaieie. ?aaeien-iioaioe?aee iae?ioeeee?/ieo eiiieaen?a CuL37 ? CuL39 aeaui ieae/?, i?ae aeey ?o aiaeiaa NuL33. Iayai?noue ienai?aeiiai o?aaiaioo a e?aaiaeao i?eaiaeeoue aei noaa?e?caoe?? i?ae?(???) ii??aiyii c eiiieaenaie c oaeei aea iaai?ii oaeaoieo oeeee?a, oi/a ?ici?? oaeaoieo oeeee?a nai ii nia? ? a?eueo nooo?aei. I?enooi?noue aaiceeueieo cai?niee?a ia aieeaa? ia aaee/eio Ef, iaeiae cai?ia iaoeeaiiai? a?oie a CuL39 ia N-iaoeeueio (CuL41), a oei a?eueoa ia aeaeo?iiiaeoeaioi?io i?o?ia?oio (CuL42), i?eaiaeeoue aei aeanoaa?e?caoe?? i?ae?(???). Ia a?aei?io a?ae i?ae?, ci?ie Af a ?yaeo eiiieaen?a NiL30-NiL35 cia/ii iaio? ((100 iA). Iaea?eueo iiceoeaieie iioaioe?aeaie oa?aeoa?ecothoueny eiiieaene c 5,6,5-iaai?ii oaeaoieo oeeee?a (NiL32 i NiL33). Iayai?noue ienai?aeiiai o?aaiaioo a e?aaiae? oaeiae i?eaiaeeoue aei noaa?e?caoe?? i?eaeth(???) ?, ia a?aei?io a?ae eiiieaen?a i?ae?, oeae oaeoi? ? a?eueo aaaeeeaei, i?ae ci?ia ?ici??o oaeaoieo oeeee?a. Ii??aiyiiy aeaieo oaae. 4 ? 1 na?ae/eoue, ui iayai?noue ai?aeieo a?oi a iieaeoeao e?aaiae?a o an?o aeiaaeeao i?eaiaeeoue aei iiieaeaiiy Ef ia?e NiIII/IIL ii??aiyii c ai?iieie nenoaiaie c oei aea iaai?ii oaeaoieo oeeee?a. Ia iniia? ?ic?aooie?a ca ??ai. (1) aeey eiiieaen?a i?eaeth c e?aaiaeaie I2L33, I2L37 ? I2L39 iiaeia c?iaeoe aeniiaee, caaaeii aiaeia?/i? oaeei aeey ai?iieo eiiieaen?a. Aeecuee?noue ??cieoeue Ef aeey NiL33 ? NiL39 oa Ni(2,3,2-tet) ? NiL1 na?ae/aoue i?i iaeiaeia? i?e?iaeo ? aaee/eio noaa?e?coth/iai aoaeoo 14-/eaiieo iae?ioeeee?a a iaio ia?ao. Aeey i?ae?(???) o an?o iae?ioeeee?/ieo e?aaiaeao oa?aeoa?ia noaa?e?caoe?y ii??aiyii c eiiieaenii CuL33, i?e/eiith yei? ? i?aeaeuaia oa?iiaeeiai?/ia no?ee?noue CuIIILioe ii??aiyii c CuIIILae. Oeae oaeo i?aeoaa?aeaeo? oaco i?i aecia/aeueio ?ieue a noaa?e?caoe?? iaoae?a(???) a?aeiia?aeiino? ?ici???a ii?iaeieie e?aaiaeo ? ?iia iaoaeo - ia a?aei?io a?ae i?eaeth(???), aeey yeiai 13-/eaiiee iae?ioeeeeo ? caiaeei, aeey i?ae?(???) a?i ? iaea?eueo i?aeoiaeyuei, ui ? ae?aaea?oueny a iaeieae/iio iioaioe?ae? ia?e CuIII/IIL37. I?e oeueiio o?eueee a 13-/eaiiiio iae?ioeeee? ia? i?noea ni?aa?aeiioaiiy Af(CuIII/IIL) ( Af(NiIII/IIL). Aiaeia?/ia ia??ai?noue a ?yaeo ML30-ML35 niinoa??aa?oueny o?eueee a eiiieaenao c 5,5,5-iaai?ii oaeaoieo oeeee?a. Niieoee IL36 aeathoue iiaeeea?noue aeine?aeeoe aieea ia ?aaeien-aeanoeaino? "ciai?oiueiai" (oiaoi ii aoiiia? eenith) i?ioiioaaiiy ai?aeii? a?oie. C io?eiaieo aeaieo aeieeaa?, ui oaeee i?ioean i?eaiaeeoue aei i?aeaeuaiiy Af ia? M???/??L (?en.5). A?aooaaiiy an?o ??aiiaaa ca o/anoth I??L36 oa I???L36, I+ ? SO42- aeicaieeei ?ic?aooaaoe aaee/eie Af eiiieaen?a c ??ciei nooiaiai i?ioiioaaiiy (oaae. 5). sse aeaeii, Af ia?e Ni???/??L36 a ia?oei?aoiiio ?ic/ei? ? i?ii?aeiei i?ae oaeeie aeey eiiieaen?a c L1 ? H2L39, iaeiae i?ioiioaaiiy ai?aeii? a?oie i?eaiaeeoue aei i?aeaeuaiiy iioaioe?aeo ia 100 iA. A iaeo?aeueiiio ?ic/ei? Af Cu???/??L36 cia/ii aeuee, i?ae aeey Cu???/??L39. Ua a?eueo aeiaeaoia cia/aiiy Af oa?aeoa?ia aeey Cu???/??(HL36), oiaoi i?aeaeuaiiy iioaioe?aeo i?e i?ioiioaaii? aeey ?en. 5. Caeaaeiino? a?ae ?I aaee/ei Ef ia? I???/??L36 aeey eiiieaeno i?eaeth a ?ic/eiao c 0,5 I NaClO4 (1) aai 0,5 I Na2SO4 (2), oa i?ae? (0,5 I NaClO4, (3)). E?ea? a?aeiia?aeathoue caeaaeiinoyi, io?eiaiei c a?aooaaiiyi ?aaeoe?e i?ioiioaaiiy oa ooai?aiiy noeueoaoieo eiiieaen?a ca o/anoth I??L ? I???L. eiiieaeno i?ae? i?eaeecii a aeaa ?ace a?eueoa, i?ae aeey i?eaeth. Oaeei /eiii, i?ioiioaaiiy ai?aeii? a?oie i?eaiaeeoue aei nooo?ai? aeanoaa?e?caoe?? iaoae?a(???), i?e/iio a?ae?iene?i?iia a?oia, yea ooai?th?oueny a ?acoeueoao? oeueiai i?ioeano, ca nai?ie aeiii?ieie aeanoeainoyie aeoaea aeecueea aei aoi?eiii? ai?iia?oie. Oaaeeoey 5. Aaee/eie Af (iA) eiiieaen?a ML a aiaeieo ?ic/eiao ?aaeien-ia?a Eiiieaen i?eaeth Eiiieaen i?ae? 0,5 I NaClO4 0,5 I Na2SO4 0,5 I NaClO4 I???/??(L1)3+/2+ 740 495 - I???/??(HL36) 3+/2+ 750 SYMBOL 177 \f "Symbol" 10 - 1160 SYMBOL 177 \f "Symbol" 10 I???/??(L36) 2+/+ 655 SYMBOL 177 \f "Symbol" 5 565 SYMBOL 177 \f "Symbol" 5 935 SYMBOL 177 \f "Symbol" 5 I???/??(L39) +/0 580 545 680 E?iaoe/i? oa?aeoa?enoeee aioo??oiueinoa?ieo ?aaeoe?e c ia?aiinii aeaeo?iia a eiiieaenao i?eaeth(???), i?ae?(???) oa eiaaeueoo(???). 2.1.E?iaoe/ia noaa?euei?noue eiiieaen?a i?eaeth(???) oa i?ae?(???) Ca i??o e?iaoe/ii? noaa?eueiino? eiiieaen?a iaoae?a(???) i?eeiaeanue oaeaee?noue ?aaeoe?e ia?oiai ii?yaeeo, ye? i?eaiaeyoue aei a?aeiiaeaiiy IIIIL a ?acoeueoao? aioo??oiueinoa?ieo (AN) ?aaeien-i?ioean?a. sse aoei aeiaaaeaii iaoiaeaie ANI oa ssI? aeey niieoe i?eaeth, i?iaeoeoaie oeeo ?aaeoe?e ? eiiieaene iaoae?a(??) c e?aaiaeaie, ui i?noyoue N=N ca’ycie. v = -d[IIIIL]/dt = k?icee [IIIIL] (2) sse na?ae/aoue io?eiai? ?acoeueoaoe, aeniiaie, ui oeeee?/ia i?e?iaea e?aaiaeo naia ii nia? ia i?eaiaeeoue aei oa?iiaeeiai?/ii? noaa?e?caoe?? i?eaeth(???), ni?aaaaeeeaee ? a?aeiinii e?iaoe/iiai aniaeoo noaa?e?caoe?? - oi/a k?icee NiIII(2,3,2-tet) aeua, i?ae NiIIIL1 (aeea. oaae.1), aiia cia/ii ieae/a, i?ae aeey eiiieaen?a aaaaoueio iaoeeueiaaieo iae?ioeeee?a (oaae.6). E?euee?noue iaoeeueieo a?oi a iae?ie?eueoe? i?aeoe/ii ia aieeaa? ia e?iaoe/io noaa?euei?noue NiIIIL, oi/a ?aaeien-iioaioe?ae eiiieaen?a ci?ith?oueny aeineoue nooo?ai (aeea. oaae.3). Ca?eueoaiiy iaiane/aiino? e?aaiaeo caaaeii i?eaiaeeoue aei e?iaoe/ii? aeanoaa?e?caoe?? iaoaeo(???). Aaaeeeaei /eiie- Oaaeeoey 6. Eiinoaioe oaeaeeino? aioo??oiueieiiieaeniiai a?aeiiaeaiiy niieoe i?eaeth(???) c oao?aacaiae?ioeeee?/ieie e?aaiaeaie a 0,1 I I2SO4 (295 E) Eiiieaen Ni???L k?icee 104, n-1 Eiiieaen Ni???L k?icee 104, n-1 NiL1, NiL19, NiL20 ( 0,01 NiL25 0,9 SYMBOL 97 \f "Symbol" -, SYMBOL 98 \f "Symbol" -, SYMBOL 103 \f "Symbol" -, SYMBOL 101 \f "Symbol" -NiL21 1,2 SYMBOL 97 \f "Symbol" -NiL27 1.7 NiL22 ( 0,1 SYMBOL 98 \f "Symbol" - Ni L27 0,6 SYMBOL 97 \f "Symbol" -, SYMBOL 98 \f "Symbol" -, SYMBOL 103 \f "Symbol" -NiL23 1,6 NiL28 9,0 SYMBOL 97 \f "Symbol" -, SYMBOL 98 \f "Symbol" -NiL24 0,1 NiL29 ( 10 eii, yeee aieeaa? ia e?iaoe/io noaa?euei?noue i?eaeth(???), ? eiioi?iaoe?y e?aaiaeo. Oae, ia?ao?ae a?ae eiiieaen?a L20 (L22) aei L21 (L23) i?eaiaeeoue aei i?aeaeuaiiy k?icee, i?e oeueiio eiio?ao?aoe?y aoiia acioo iaeaea ia aieeaa? ia oeae ia?aiao?. Ca?eueoaiiy e?eueeino? Naeeno a iae?ioeeee? i?eaiaeeoue aei iiieaeaiiy e?iaoe/ii? noaa?eueiino? eiiieaen?a i?eaeth(???) (oaae.7), ui ei?aeth? c i?aeaeuaiiyi Af ia?e NiIII/IIL. A?aei?iiino? a aoaeoeaieo aeoeaaoe?eieo ia?aiao?ao i?ae NiIIIL8 oa NiIIIL1 ? NiIIIL3 iiaeia iiynieoe ??cieie ?aaeoe?eieie oi?iaie, a yeeo a?aeaoaa?oueny ?aaeien-i?ioean: aeey NiIIIL9 oea ae?aeaaeiiieaen, oiae? ye aeey NiIIIL1 ? NiIIIL3 oea, oaeaeoa ca ana, aaeoeoe c ieniai?iiaie. Oaaeeoey 7. E?iaoe/i? ia?aiao?e ((I# a eAeae/iieue, (S# a Aeae/iieue E) aioo??oiueieiiieaenieo ?aaeoe?e ca o/anoth acaoeeeeaiiaeo eiiieaen?a i?eaeth(???) Eiiieaen Na?aaeiaeua Af, iA k?icee105, n-1 (295 E) (I# (S# Ni???L1 oinoaoiee aooa? 0,1 I IClO4 480 510 34 30 93 92 -15 -19 Ni???L3 oinoaoiee aooa? 0,1 I IClO4 510 540 39 50 92 94 -18 -11 Ni???L8 oinoaoiee aooa? 0,1 I IClO4 540 560 61 83 102 100 +20 +18 Ine?eueee ANI eiiieaen?a iaoae?a(???) c ai?aeai?nieie e?aaiaeaie H2L ia aoee iienai?, oeyoii niaeo?ioioiiao?e/iiai oeo?oaaiiy ca aeiiiiiaith K4Fe(CN)6 aoee anoaiiaeai? iaiao?aei? aeey e?iaoe/ieo aeine?aeaeaiue iiey?i? eiao?oe??ioe ?o nioa iiaeeiaiiy. Oaeaee?noue cieeiaiiy eiiieaen?a I???L+ caeaaeeoue a?ae ?I ? i?e?iaee aooa?ieo noi?oae, oiio aeine?aeaeaiiy ?o e?iaoe/ii? noaa?eueiino? aoee i?iaaaeai? aai a aeineoue eeneeo ?ic/eiao, aai a “iaeo?aeueieo” oiiaao, eiee aooa?ii neoaeea nai eiiieaen. A a?eueoino? aeiaaee?a ?aaeoe?? iaee ia?oee ii?yaeie o a?aeiia?aeiino? c ??ai. (2). C?noaaeaiiy aaee/ei k?icee (oaae.8) c? cia/aiiyie Af ia?e IIII/??L (aeea. oaae. 4) na?ae/eoue, ui caaaeii niinoa??aa?oueny ei?aeyoe?y i?ae e?iaoe/iith ? oa?iiaeeiai?/iith noaa?euei?noth eiiieaen?a - ca?eueoaiiy Af i?eaiaeeoue aei i?aeaeuaiiy k?icee (?en.6). Oaaeeoey 8. Eiinoaioe oaeaeeino? (n-1 i?e 298 E) ? aeoeaaoe?ei? ia?aiao?e ((H( a eAeae/iieue, (S( a Aeae/iieue E) ?aaeoe?e ?iceeaaeo eiiieaen?a I???L ?en. 6. Ei?aeyoe?y i?ae e?iaoe/iith noaa?euei?noth eiiieaen?a IIIIL a iaeo?aeueieo ?ic/eiao oa aaee/eiaie iioaioe?ae?a ia? IIII/??L (a 0,1 I NaClO4) aeey eiiieaen?a i?eaeth (() oa i?ae? (() (oeeo?e a?aeiia?aeathoue iiia?o e?aaiaeo). ?en. 7. Ei?aeyoe?eia ae?aa?aia i?ae aeoeaaoe?eieie ia?aiao?aie ?aaeoe?e ?iceeaaeo eiiieaen?a NiIIIL (() oa CuIIIL (() a iaeo?aeueieo ?ic/eiao (oeeo?e a?aeiia?aeathoue iiia?o e?aaiaeo). sse aeaeii c ?en.6, oaeaee?noue ?iceeaaeo eiiieaen?a i?eaeth(???) a?eueo /ooeeaa aei aaee/eie Af, i?ae eiiieaen?a i?ae?(???). Aeioe?eueii oaeiae a?aecia/eoe, ui aaee/eie k?icee aeaio eiiieaen?a 13-/eaiieo iae?ioeeee?a (Ni???L37 ? Ni???L43) a?ae??ciy?oueny ia 6 ii?yaee?a. Noiniaii aeoeaaoe?eieo ia?aiao??a iiaeia noaa?aeaeoaaoe, ui c? ca?eueoaiiyi aioaeuei?? aeoeaaoe?? aio?ii?y noa? iaio a?ae’?iiith (?en.7). Iaea?eueoeie cia/aiiyie (I( ? (S( na?aae niieoe i?eaeth oa?aeoa?ecothoueny eiiieaene, a yeeo iayai? o?e 5-/eaii? oaeaoi? oeeeee (NiIIIL30, NiIIIL31, NiIIIL43), oiae? ye c oi/ee ci?o aaee/ei aeoeaaoe?eieo ia?aiao??a aiaeia?/i? eiiieaene i?ae?(???) (CuIIIL30, CuIIIL31, CuIIIL37 ? CuIIIL38) ia a?ae??ciythoueny i?eioeeiiai a?ae ?ioeo niieoe. A?aoiaoth/e, ui naia a oeeo nenoaiao ?ii i?eaeth(???) iiaea aeoiaeeoe c ii?iaeieie e?aaiae?a, a oie /an ye iaioee ?ii i?ae?(???) aoiaeeoue a ia?, oea aeicaiey? c?iaeoe i?eiouaiiy i?i iayai?noue ca’yceo i?ae aeaoi?iaoe??th o?iiioi?a ?iia i?eaeth(???) ? aeoeaaoe?eieie ia?aiao?aie ?aaeien-?aaeoe?e ca eiai o/anoth. I?e aiae?c? e?iaoe/ii? iiaaae?iee eiiieaen?a I???L a eeneeo na?aaeiaeuao iaiao?aeii iaoe ia oaac?, ui a?aeiiaeaiiy iaoaeo(???) iiaea i?ioiaeeoe a /anoeao, ye? a?ae??ciythoueny nooiaiai i?ioiioaaiiy (noaia 1). Noaia 1 ?aaeien-?iceeaae eiiieaen?a i?ae?(???) a ae?aiacii? 0,2 ( ?I ( 2,5 i?aeei?ythoueny e?iaoe/iiio ??aiyiith (2), i?e/iio oaeaee?noue i?ioean?a i?aeaeuo?oueny c? ciaioaiiyi ?I. Oea na?ae/eoue i?i c?inoaiiy aeeaae?a k1 ? k2 a caaaeueio oaeaee?noue ?iceeaaeo ? i?i oa, ui e?iaoe/ia noaa?euei?noue i?ioiiiaaieo oi?i ieae/a, i?ae CuIIIL+. Caaaeii ia? i?noea ianooiiee ii?yaeie i?aeaeuaiiy e?iaoe/ii? noaa?eueiino? eiiieaen?a i?ae?(???) (a aeoaeeao i?eaaaeaia k?iceeo 10-3, n-1 i?e ?I=1) CuL41 (13,3) ( CuL33 (7,55) ( CuL39 (6,46) ( CuL37 (3,53) ( CuL40 (2,13) ( CuL38 (0,763) ( CuL31 (0,193) ( CuL30 (0,064). A?i aeaui a?ae??ciy?oueny a?ae iine?aeiaiino?, ciaeaeaii? aeey iaeo?aeueieo ?ic/ei?a (aeea. oaae.8). Oaea iniaeea?noue iiaea aooe aeeeeeaia naia aianeaie ?aaeoe?e i?ioiiiaaieo oi?i eiiieaen?a, ui i?aeoaa?aeaeothoue ? io?eiai? a eeneeo na?aaeiaeuao aeoeaaoe?ei? ia?aiao?e ?aaeoe?e ?iceeaaeo CuIIIL37 (67 eAeae/iieue;-49 Aeae/iieue K), CuIIIL38 (78;-24), CuIIIL39 (71;-31) ? CuIIIL40 (69;-47), ye? i?eioeeiiai a?ae??ciythoueny a?ae oaeeo aeey iaeo?aeueieo ?ic/ei?a (ii??ai. c aeaieie oaae. 8). A neeo aeui? i?ae aeey i?ae?(???) e?iaoe/ii? noaa?eueiino? ?aaeien-?iceeaae eiiieaen?a NiIIIL aoa aeine?aeaeaiee i?e ?I(1. I?e oeueiio aeey an?o eiiieaen?a, ca aeiyoeii NiIIIL35, niinoa??aa?oueny ca?eueoaiiy k?icee c i?aeaeuaiiyi eeneioiino?. A oei?iieeneeo ?ic/eiao k?icee i?aeoe/ii e?i?eii caeaaeeoue a?ae eiioeaio?aoe?? i?ioii?a aeey an?o eiiieaen?a, e??i NiIIIL33. Aeey oeeo niieoe ia? i?noea ianooiia iine?aeiai?noue e?iaoe/ii? noaa?eueiino? (a aeoaeeao i?eaaaeai? k?icee 104, n-1 a 1.0 I INlO4): NiL33 (49,4) ( NiL41 (1,88) ( NiL40 (1,45) ( NiL35 (1,34) ( NiL30 (0,359) ( NiL39 (0,220) ( NiL32 ( NiL43 (0,179). Oeae ?yae aeineoue nooo?ai a?ae??ciy?oueny a?ae io?eiaiiai a iaeo?aeueieo ?ic/eiao (aeea. oaae.8), oi/a iaea?eueo e?iaoe/ii noaa?euei? eiiieaene NiIIIL35, NiIIIL39 ? NiIIIL43 caeeoathoueny oaeeie ? a eeneeo na?aaeiaeuao. Ca?eueoaiiy eiioeaio?aoe?? H2SO4 i?eaiaeeoue aei e?i?eiiai i?aeaeuaiiy oaeaeeino? ?iceeaaeo NiIIIL39, NiIIIL41 ? Ni2IIIL45, oi/a aeey ?ioeo niieoe ia? i?noea a?aeoeeaiiy a?ae e?i?eiino?, a aeey NiIIIL32, NiIIIL33, ? NiIIIL40 caeaaei?noue k?icee a?ae [H2SO4] aeoiaeeoue ia ieaoi. Oe? aeai? na?ae/aoue i?i eii?aeeiaoe?th noeueoao-?ii?a aei i?eaeth(???), ia eiinoaioo ??aiiaaae yei? aieeaa? aoaeiaa aeaaoi??aeueiiai e?aaiaeo. 2.2. Oioi?iaeoeiaai? ?aaeien-i?ioeane a oao?aaiiaeueieo aoeeaeioao?aai?iieo eiiieaenao eiaaeueoo(???) Aeeaoeeaeioao?aai?ii? eiiieaene eiaaeueoo(???) ? e?iaoe/ii ?ia?oieie a ?aaeoe?yo aioo??oiueieiiieaeniiai ia?aiino aeaeo?iia, oiio aeey aeoeaaoe?? oaeeo i?ioean?a iaiao?aeia caoaeaeaiiy iieaeoe, iai?., oeyoii ii?ii?iaiiy. Ia’?eoaie aea/aiiy aieeao i?e?iaee aen?aeueieo e?aaiae?a ia ?aaeien-aeanoeaino? eiiieaen?a aoee oao?aaiiaeuei? niieoee o?ain-[Co???LXY]n+. aea L - L20 aai L27, a O=Y=Cl-, Br-, NCS-, NCO-, N3-, NO2-, CN-, aai O=Cl-, Y=NCO-, NCS-, N3-, H2O, O=Br-, Y=NCS-, H2O. Ii?ii?iaiiy eiiieaen?a a nioaao iiaeeiaiiy d-d ia?aoiae?a ia i?eaiaeeoue aei ?aaeien-ia?aoai?aiue. ?acii c oeei, caoaeaeaiiy niieoe a OO ae?aiacii? (aea i?iyaeythoueny NICN(Co(III) oa iaio aia?aaoe/i? (- ? (-NICO(Co(III)) noi?iaiaeaeo?oueny ?aaeien-?aaeoe?yie. Ia?aa?a oeeo i?ioean?a caeaaeeoue a?ae i?e?iaea ?ic/eiieea. Oae, i?e ii?ii?iaii? aiaeieo ?ic/ei?a eiiieaen?a eiaaeueoo(???) (ii?=39 370 ni-1 ia? i?noea eeoa oioiaeaaoaoe?y. A 12 I INl niinoa??aa?oueny cieeiaiiy [CoLX2]+ ? iiyaa [CoIICl4]2-, i?e/iio ca ca?eueoaiiyi aaee/eie 103(Ni(??) aen?aeuei? e?aaiaee iiaeia ?ici?noeoe o iine?aeiaiino? Br- (1,3) ( N3- (1,5) ( NO2- (1,7) ( NCS- (2,1)( Cl-(2,3) ( CN- (2,4) ( NCO- (3,8), yea ei?aeth? c ia?aiao?aie ?o oeen-aieeao. A??ia?aeii, a oeeo i?ioeanao ia? i?noea ia?aiin aeaeo?iia c iae?ioeeee?/iiai e?aaiaeo ia eiaaeueo(???) c ianooiiei a?ae?ie?cii i?aai?/iiai i?iaeoeoo. Cian?i ?ioa oioio?-i?/ia iiaaae?iea oa?aeoa?ia aeey eiiieaen?a eiaaeueoo(???) a iaaiaeieo ?ic/eiieeao, aea ia ia?aa?a i?ioean?a aieeaa? i?enooi?noue eenith. OO ii?ii?iaiiy eiiieaen?a [CoLOY]n+ a iaoaiie? a aiaa?iaieo oiiaao i?eaiaeeoue aei ?o cieeiaiiy ? iiyae eiiieaen?a CoIIL. Cai?ia iaoaiieo ia ?io? nie?oe iaei aieeaa? ia aoaeoeai?noue oioii?ioean?a. A AeINO eaaioiaee aeo?ae eiiieaeno CoIIL cia/ii ieae/ee, a oioie?c a ACN i?eaiaeeoue aei ooai?aiiy oao?aaae?e/iiai eiiieaeno eiaaeueoo(??) [Co(Cl)n(ACN)4-n](2-n)+. Aiae?c ?aaeoe?eieo noi?oae i?ney oioie?co cana?ae/ea, ui a iaoaiieueieo ?ic/eiao ii?yae c CoIIL ooai?th?oueny oi?iaeueaeaa?ae ? i?ioiie, i?e oeueiio ni?aa?aeiioaiiy i?iaeoeo?a caeaaeeoue a?ae i?e?iaee O- (oaae. 9). A niaeo?? AI? ii?ii?iaiiai caii?iaeaiiai ?ic/eio CoL27Cl2+ niinoa??aa?oueny noia?iiceoe?y neaiae?a eiiieaeno CoIIL27 (gII=2,016) ? ?aaeeeaeo NI2II (gII = 2,004, A=0,0017 On). Aeoiaey/e c oiia aenia?eiaioo ? io?eiaieo aeaieo iiaeia noaa?aeaeoaaoe, ui iaea?eueo a??ia?aeiei o aea/aieo nenoaiao ? ia?aiin aeaeo?iia c aen?aeueiiai e?aaiaeo ia eiaaeueo(???), yeee i?eaiaeeoue aei iine?aeiaiino? ?aaeoe?e, iieacaieo ia noai? 2. Ia?aeiia ?aaeeeaeueia ia?a {CoIILX,X.} aoaeoeaii ?aeiia?io? a eii??oe? ?ic/eiieea, oiio aeey i?aeaeuaiiy aeoiae?a i?iaeoeo?a iaiao?aei? ?aaaaioe-eiieo?aioe, iai?., nie?oe (??ai.3). ?ioa iiaeeea?noue aeaaaeaiiy ?aaeeeae?a O. c i?ioean?a ?aeiia?iaoe?? iieacaia ??ai. 4 noaie 2. Oa- Oaaeeoey 9. Eaaioia? aeoiaee oioi?aaeien-?aaeoe?e eiiieaen?a eiaaeueoo(???) oeio [CoLX2]+ a iaoaiie? ((ii?=30770 ni-1) L X Aiaa?iaiee oioie?c a) Aa?iaiee oioie?c a) (Co(II) (CH2O (Co(II) (CH2O L20 Cl- 0,11 0,053 (0,01 0,056 Br- 0,081 0,042 (0,01 0,046 NCO- 0,037 0,013 a) 0,012 NCS- 0,007 0,001 0,048 0,004 N3- 0,085a) 0,017a) 0,13 0,069 L27 Cl- 0,35 0,16 (0,01 0,050 Br- 0,11 0,050 (0,01 0,022 NCO- 0,11 0,030 0,055 0,032 NCS- 0,06 0,002 0,070 0,005 N3- 0,20 0,015 0,29 0,080 I?ei?oea: a) oi/i?noue aecia/aiiy ( ( 15%; a) oi/i?noue aecia/aiiy ( ( 20%; a) eaaioiaee aeo?ae ia aecia/aany; a) oi/i?noue aecia/aiiy ( ( 25%. Noaia 2 eee oeyo a?aenooi?e aeey aaeiaai?aeieo ?aaeeeae?a, aea aoaeoeaiee aeey ?ioeo /anoie, iai?., ooai?aiiy acioo a ?acoeueoao? ?iciaaeo ?aaeeeaea aceaeo. E?iaoe/iee aiae?c noaie 2 cana?ae/ea, ui ?aaeoe?? 7 oa 8 iiaeia ia i?eeiaoe aei oaaae, oiio caaaeueio oioi?aaeoe?th eiiieaen?a [CoLX2]+ i?e X=Cl- aai Br- iiaeia caienaoe ye h( 2[CoIIILX2]+ + CH3OH = 2CoIIL2+ + CH2O + 2H+ + 4X- (3) ui aeia?a ocaiaeaeo?oueny c a?aeiioaiiyi (Ni(??):(NI2I=2:1. I?e e?aaiaeao, aeey yeeo iiaeeeaa ?aaeoe?y 4, a?aeiioaiiy (Ni(??)/(NI2I iiaeiii ciaiooaaoenue, ui ae?enii ia? i?noea o aeiaaeeao O-= N3, NCS ?, /anoeiai, NCO (aeea. oaae. 9). Caaaeii (Ni(??) ciaioo?oueny a ?yaeo Cl- ( N3- ( Br- ( NCO- ( NCS- neiaaoii ciaioaiith aeaeo?iiiaeiii?ieo aeanoeainoae aen?aeueieo e?aaiae?a. Iiae?aia iine?aeiai?noue N3- (0,40; 0,16) ( Nl- (0,35; 0,16) ( I2I (0,27; 0,05) ( NCO- (0,21; 0,07) ( NCS- (0,035; 0,015) (a aeoaeeao i?eaaaeai? (Ni(??) ? (NI2I) oa?aeoa?ia ? aeey ?aaeoe?e ianeiao?e/ieo eiiieaen?a [NiL27Nl(Y)]n+, iaeiae a oeueiio aeiaaeeo aaee/eie ( iaiao?aeii o?aeooaaoe ye ioe?ii/i? ?c-ca ia?aeaeueiiai ia?aa?ao ?aaeoe?e nieueaie?co. Oioie?c iaoaiieueieo ?ic/ei?a [NiLO2]+ (O=Cl, Br) a i?enooiino? eenith ia noi?iaiaeaeo?oueny ooai?aiiyi NiIIL, oi/a a ?ic/ei? iaeiie/o?oueny NI2I (aeea. oaae. 9) oa I2I2. Iaeiae oa, ui a niaeo?ao AI? niinoa??aathoueny neaiaee NiIIL ? ?o eeniaaeo aaeoeo?a, aeicaieythoue ?icoe?eoe noaio 2 ?aaeoe??th NiIIL2++I2 ( [NiLX2]+ +H2O2. Ia a?aei?io a?ae aaeiaai?aeieo, oioie?c aceaeieo aai ?iaeai?aeieo niieoe noi?iaiaeaeo?oueny a?aeiiaeaiiyi aeo?aeiiai eiiieaeno, i?e/iio (Ni(??) oa (NI2I a oaeeo i?ioeanao iaa?oue aeu?, i?ae aac I2. A??ia?aeii, i?e iayaiino? eenith c’yaey?oueny aeiaeaoeiaee oeyo cieeiaiiy ?aaeeeae?a N3. (aai NCS.) - ?o aca?iiae?y c I2 c ooai?aiiyi i?iaeoeo?a, caeaoieo ieenithaaoe iaoaiie aei NI2I. Oaeei /eiii, i?e oioie?c? [NiLX2]+ a aa?iaieo oiiaao ia? i?noea ye a?aeiiaeaiiy eiaaeueoo(???) aei NiIIL, oae ? ieeniaiiy inoaiiueiai eeniai. I?e oeueiio caaaeueiee oioii?ioean i?e O-=Cl, Br iieno?oueny ye ieeniaiiy iaoaiieo eeniai, yea eaoae?co?oueny eiiieaenaie [NoLX2]+ [NoLX2]+, h( CH3OH + O2 ( CH2O + H2O2 (4) Aiaeia?/io oioio?i?/io iiaaae?ieo i?iaeaiiino?oaaee ? eiiieaene eiaaeueoo(III) c iae?ia?oeeee?/ieie e?aaiaeaie L47-L49, iaeiae caaaeii aeey ieo oa?aeoa?ia cia/ii ieae/a oioiaeoeai?noue (a aiaeieo ?ic/eiao (Ni(??)L ( 0,002 i?e ii?ii?iaii? a NICN(Co(III)). Oea iiynith?oueny iaiiaeeea?noth ia?aoiaeo ia?aeiii? ?aaeeeaeueii? ia?e a ia’?i ?ic/eiieea, ine?eueee i?ae ?? eiiiiiaioaie ?nio? o?i?/iee ca’ycie. Iayai?noue a ?aaeoe?ei?e noi?o? iaoaiieo i?eaiaeeoue aei i?aeaeuaiiy aaee/ei (, i?e oeueiio ii?yae c ooai?aiiyi Ni??L iaeiie/o?oueny NI2I o ni?aa?aeiioaii? 2:1 ? aeae?eythoueny i?ioiie. I?e aa?iaiiio oioie?c? eaaioia? aeoiaee Ni??L ye a aiaeieo, oae ? a aiaeii-iaoaiieueieo noi?oao aeoaea iecuee?, a oie /an ye aaee/eie (NI2I i?aeoe/ii ia caeaaeaoue a?ae iayaiino? I2. A oe?eiio, aeey iieno iiaaae?iee iae?ia?oeeee?/ieo eiiieaen?a oe?eeii i?eaeaoia iine?aeiai?noue ?aaeoe?e noaie 2, a ye?e ?ieue ?aaeeeaeueii? /anoee O. a?ae?a?a? N-?aaeeeae iae?ia?oeeee?/iiai e?aaiaeo. Aeoiaey/e c oeueiai, noia?io oioi?aaeien-?aaeoe?th a aiaa?iaieo oiiaao iiaeia caienaoe ??aiyiiyi, aiaeia?/iei ??ai. (3), a a i?enooiino? eenith - ??ai.(4). 2.3. ?aaeoe?? aioo??oiueieiiieaeniiai ia?aiino aeaeo?iia a iyoeeii?aeeiiaaieo eiaaeueo(???)aee?eueieo eiiieaenao Aeey aeine?aeaeaiiy aeanoeainoae i?aaiieiaaeueoiaeo(???) eiiieaen?a aoee aea?ai? 5-eii?aeeiiaai? niieoee RNi???L (aea L=H2L50- H2L57, aeea. ?en.1), a yeeo aoaeiaa noi?yaeaieo e?aaiae?a L ? i?aai?/iiai o?aaiaioa R (R=Me, Et, Ph) caiaeeoue aei i?i?ioio noa?e/i? aca?iiae?? i?ae ieie. sse na?ae/aoue aeaeo?io?i?/i? aeine?aeaeaiiy (oaae.10), cai?ia aoeeaiiaiai (en) i?noea a e?aaiae? ia oai?eaiiaee (phen) ?/aai ia?ao?ae a?ae iae?ioeeee?/ieo N4- aei a?aee?eoieaioethaiaeo N2O2-niieoe noi?iaiaeaeo?oueny aiiaeiei cnoaii aaee/ei Af ca aeiyoeii iioaioe?aeo ia?e NiIII/IIL, aea ia? i?noea i?aaethth/ee aieea eii?aeeiaoe?? ?ic/eiieea. A??ia?aeii, oea ca’ycaii c? cieaeaiiyi aia?a?? (-aeoeaioi?ii? II ? iineeaiiyi (-aeaoeaii? aca?iiae?? Ni-L. ?acii c oei, aaee/eie Af RNoIII/IIL a?eueo i?ae ia 1500 iA(!) cnoioo? a eaoiaeio iaeanoue ii??aiyii c NoIII/IIL. A eiaaeueo-aee?eueieo eiiieaenao aaeaeinue oaeiae ca?a?no?oaaoe ?aaeien-ia?ao?ae RNoIV/IIIL, a oie /an ye a NiL a?i a?aeaoaa?oueny i?e iioaioe?aeao, a?eueo iiceoeaieo, i?ae iioaioe?aee ieeniaiiy e?aaiae?a. Aeniiaie i?i aaoaioe/i?noue e?iaoe/ii noaa?eueii? niieoee eiaaeueoo(IV) aoa i?aeoaa?aeaeaiee iaoiaeii AI?. Oaaeeoey 10. ?aaeien-iioaioe?aee (iA) eiiieaen?a eiaaeueoo a aoeaoii?o?eeueieo ?ic/eiao oa iaoeeeiaaeueoo a AeIOA (296 E) Eiiieaen ?aaeien-ia?ao?ae Eiiieaen ?aaeien-ia?ao?ae NoII/IL NoIII/IIL RNoIII/IIL RNoIV/IIIL CoL50 -1680 (70) 190 (110) IaCoL50 -1770a) 210 (85) CoL51 -1400 (60) 200 (90) IaCoL51 -1840a) 530 (85) CoL52 a) 160 (85) MeCoL52 -1760a) 890 (70) CoL53 -1250 (115) 180 (85) MeCoL53 -1620a) 560 (100) CoL54 -1050 (85)a) 190 (85) MeCoL54 -1480a) 670 (70) CoL55 -960 (75); 185 (375) MeCoL55 -1460 (185) 880 (115) CoL56 -1040 (95)a) 750a) MeCoL56 -1480a) 1010 (100) CoL57 -520 (295) 160 (315) MeCoL57 -1440 (115) 990 (80) I?ei?oee: a) iaiai?ioi?e i?ioean, i?eaaaeaii cia/aiiy aiiaeiiai i?ea; a) ia aei??thaaeenue; a) a AeIOA. Oioio?i?/i? ?aaeien-?aaeoe?? eiiieaen?a aee?eeiaaeueoo(???). A ANI aeaieo niieoe iayaia nioaa ICR(Co(III). a iaeano? 14 000-16 000 ni-1 (( ( 500 - 3000 I-1 ni-1), iaeneioi yei? aaoio?iiii cnoaa?oueny i?e cai?iao -C(O)Et(-C(O)Me, phen ( en, aai N2O2 ( N4. Ii?ii?iaiiy aaicieueieo ?ic/ei?a RCoL a oe?e nioc? i?eaiaeeoue aei ?iceeaaeo eiiieaen?a aiane?aeie aiiie?oe/iiai ?ic?eao ca’yceo Ni-R. Oe? i?ioeane iiaeia a?aeia?aceoe a ?aieao iiaeae? ?aaeeeaeueieo ia? noaiith 3. Noaia 3 A caeaaeiino? a?ae oiia ? aoaeiae eiiieaen?a niinoa??aaeinue ooai?aiiy ??cieo i?iaeoeo?a. Oae, aiaa?iaiee oioie?c IaNiL50, EtCoL51, MeCoL53 ? MeCoL55 i?eaiaeeoue aei ooai?aiiy NiIIL, oiae? ye a i?enooiino? I2 a?eueo?noue niieoe ooai?ththoue ia?ienieiiieaene ROO-Co???L. Iaeiaioith oioi/ooeea?noth oa?aeoa?eco?oueny PhCoL51. Aeno?aiieyoe?y caeaaeiino? (Ni-N a?ae (ii? aei (Ni-N =0 aeicaieeea aecia/eoe ii?iaia? aia?a?? oioiaiiie?co, ui aei??aiththoue (a eAeae/iieue) 128 (MeCoL50), 143 (MeCoL51), (145 (MeCoL52), (168 (MeCoL54), 132 (MeCoL55) oa (161 (MeCoL57). ?ioeie neiaaie, cai?ie en ( phen aai N4 ( N2O2 i?eaiaeyoue aei i?aeaeuaiiy Aii?ia. Oe? no?oeoo?i? ci?ie noi?iaiaeaeothoueny oaeiae ciaioaiiyi aaniethoieo cia/aiue (Ni-N i?e ii?ii?iaii? eiiieaen?a ia iaeneioi? NICR(Co (ii??ai., 0,179 aeey IaNiL50; 0,042 aeey IaNiL51 ? 0,053 aeey IaNiL55). Oe? a?aei?iiino? iiaeia iiynieoe ??cieie aaee/eiaie k2 ?aaeoe?e ?aeiia?iaoe?? ?aaeeeaeueieo ia?. Oa?i?/i? ?aaeien-?aaeoe?? eiiieaen?a aee?eeiaaeueoo(???). A ?aieao iiaeae? ?aaeeeaeue-ieo ia? (noaia 3) aeia?a iieno?oueny oaeiae oa?iie?c eiiieaen?a RNo???L. Iayai?noue eenith iaei aieeaa? ia ia?aa?a i?ioean?a ? a?aei?iiino? i?ae aa?iaiei oa aiaa?iaiei aiiie?cii caiaeyoueny aieiaiei /eiii aei ciaioaiiy kniin a ae?oaiio aeiaaeeo. E?iaoe/i? e?ea? oa?iie?co iienothoueny ??ai. (2), ui aeicaieeei ?ic?aooaaoe kniin (oaae. 11). Io?eiai? aaee/eie eiinoaio na?ae/aoue, ui ci?ie no?oeoo?ieo ia?aiao??a e?aaiae?a L iathoue a ?aaeoe?yo oa?iie?co oaeee aea aieea ia i?oei?noue ca’yceo Ni-R, ye ? a oioio?i?/ieo i?ioeanao. Oa?iie?c aee?eeiaaeueoiaeo eiiieaen?a a aaeiaaiai?nieo ?ic/eiieeao oaeiae iieno?oueny ??ai. (2) ? e?iaoe/i? oa?aeoa?enoeee oeeo ?aaeoe?e i?eaaaeai? a oaae. 12. A oie aea /an, ia?aa?a ?aaeoe?e ca o/anoth MeCoL50 ? RCoL51 a CHCl3 ? CCl4 a?ae??ciy?oueny a?ae aiaeia?/ieo ?aaeoe?e a a?iiaoe/ieo aoaeaaiaeiyo. A oeeo aeiaaeeao c?aco ae i?ney noaae?? aiiie?co ca’yceo Ni-N ia? i?noea ooai?aiiy ClCoIIIL ((ueaen(14 000 ni-1) a ?acoeueoao? aca?iiae?? CoIIL c ?ic/eiieeii. Aeiaeaoeia? aeine?aeaeaiiy iiea Oaaeeoey 11. E?iaoe/i? ia?aiao?e (kniin a n-1, (H( a eAeae/iieue, (S( a Aeae/iieue E) ?aaeoe?e oa?iie?co RCoIIIL a a?iiaoe/ieo aoaeaaiaeiyo Eiiieaen Oieoie Aaicie Eiiieaen Oieoie Aaicie MeCoL50 3,4 10-3 (80; -70) 6,0 10-4 MeCoL54 5,5 10-6 - EtCoL51 - 5,1 10-4 (106; +7) MeCoL55 2,2 10-4 (108; -15) 1,0 10-5 MeCoL51 8,5 10-5 3,6 10-5 MeCoL56 5,0 10-5 - MeCoL52 5,1 10-5 - MeCoL57 7,1 10-5 - I?ei?oea: kniin i?e 356 E a oieoie? oa i?e 333 E a aaicie?. Oaaeeoey 12. Eiinoaioe oaeaeeino? ? aeoeaaoe?ei? ia?aiao?e ?aaeoe?e ((H(niin a eAeae/iieue, (S(niin a Aeae/iieue E) oa?iie?co RCoIIIL a oei?ai?nieo ?ic/eiieeao Eiiieaen kniin, n-1 Eiiieaen kniin, n-1 CHCl3, 313 E CCl4, 323 E CHCl3, 313 E CCl4, 323 E MeCoL51 7,2 10-4 (77; -63) - MeCoL54 ( 10-5 - EtCoL51 2,5 10-4 (78; -68) - MeCoL55 3,3 10-5 (87; -67) 4,4 10-4 (80; -64) caee, ui na?aae an?o niieoe o?eueee Co??L50 ? Co??L51 ?aaaothoue c CHCl3 oa NNl4 a aaicie? c oeiiaeie aeey a?iieaeoey?ieo anioe?aoeaieo i?ioean?a iaaaoeaieie aio?ii?yie aeoeaaoe?? (a aeoaeeao i?eaaaeai? kao a e/iieue(n i?e 300 K, (H(ao a eAeae/iieue ? (S(ao a Aeae/iieue E):CoL50+CHCl3 (1,8 10-4, 32, -213); CoL50+CCl4 (1,8 10-2, 29, -183); CoL51+CHCl3 (1,6 10-5, 55, -152); CoL51+CCl4 (1,6 10-2, 42, -140). Niaoeeo?/io iiaaae?ieo i?iyaey? eiiieaen MeCoL50, ?iceeaae yeiai a CHCl3 ? CCl4 ? aaoieaoae?oe/iei. I?e oeueiio aeiaaaea a ?ic/ei Co??L50 i?enei?th? ?aaeoe?th ?iceeaaeo MeCoL50. Aiae?c caeaaeiino? ii/aoeiai? oaeaeeino? oa?iie?co MeCoL50 a?ae eiioeaio?aoe?e ?aaaaio?a cana?ae/ea caeaaei?noue, yea iieno? noeoii?noue aeaio ia?aeaeueieo ?aaeoe?e: “eeane/iee” oa?iie?c (kA) ? ?aaeoe?th ca o/anoth ?ic/eiieea (kA), oiaoi kniin = kA + kA d[MeCoL50]/dt = (kA+kA[RX]) [MeCoL50] (RX = CHCl3 aai CCl4) (5) Aeoiaey/e c oeueiai aoea cai?iiiiiaaia iine?aeiai?noue noaae?e, ui iieno? aaoieaoae?oe/iee oa?iie?c (noaia 4), yea aoea i?aeoaa?aeaeaia iaoaiaoe/iei iiaeaethaaiiyi i?ioeano. Oaeei /eiii, i?iaaaeai? aeine?aeaeaiiy cana?ae/eee, ui c oi/ee ci?o e?iaoe/ii? noaa?eueiino? ye a a?iiaoe/ieo, oae ? a oei?ai?nieo ?ic/eiieeao ?icoe?aiiy nenoaie (-noi-?yaeaiiy a e?aaiae? L ?/aai ia?ao?ae a?ae N4- aei N2O2-oeio eii?aeeiaoe?? i?eaiaeeoue aei noaa?e?caoe?? aen?aeueiiai ca’yceo Ni-N, ui ae?aaea?oueny a ciaioaii? kniin ?aaeoe?? aiiie?co. Nooo?aith a iiaaae?ioe? aeaieo nenoai ? aca?iiae?y ia?aeiieo i?iaeoeo?a c ?ic/eiieeii, ui i?eaiaeeoue aei iaaaoeaieo aaee/ei aio?ii?e aeoeaaoe?? i?ioean?a oa?iie?co. Noaia 4 Eiiieaene eiaaeueoo ye eaoae?caoi?e ia?aaea/? eaioethaa (EIE) c iie?ia?a ia iiiiia? a ?aaeeeaeuei?e iie?ia?ecaoe?? a?i?eiaeo iiiiia??a. Eeth/iaith noaae??th ae?? caaaeaieo aeua eaoae?caoi??a ? aca?iiae?y iie?ia?iiai ?aaeeeaeo c eiiieaenii eiaaeueoo(??), ui i?eaiaeeoue aei eiaaeueo-aee?eueii? niieoee, yea ?iceeaaea?oueny ca iaoai?ciii (-ae?i?ioaaiiy, i?eaiaey/e aei ia?aaeeeaeueiiai i?iaeoeoo c oa?i?iaeueiith a?i?eueiith a?oiith oa a?ae?eaeiiai eiiieaeno eiaaeueoo(???). I?ioean i?iaeiaaeo?oueny ca ?aooiie aca?iiae?? inoaiiueiai c iiiiia?ii, a ?acoeueoao? /iai ooai?th?oueny ?aaeeeaeueiee i?iaeoeo a?ae?oaaiiy, yeee ii/eia? iiaee eaioetha iie?ia?ecaoe??. C iaoith iiooeo iiaeo EIE ? oi?ioethaaiiy iniiaieo aeiia aei aoaeiae oaeeo niieoe, a oaeiae a?aoiaoth/e, ui eeth/iaeie noaae?yie a i?ioean? eaoae?co ? ooai?aiiy oa aiiie?oe/iee ?ic?ea ca’yceo eiaaeueo-aoaeaoeue, aoea aeine?aeaeaia iiaaae?ieo a ?aaeoe?yo iie?ia?ecaoe?? eiiieaen?a eiaaeueoo, aeanoeaino? yeeo iaaiai?thaaeenue aeua. Caaaeii, a yeino? iioaioe?eieo EIE aoa aea/aiee oe?ieee iaa?? eiiieaen?a Eaoae?oe/iee aoaeo a ia?aaea/? eaioethaa i?iyaeee eeoa CoL51, CoL54 oa CoL61, oiae? ye an? eao?iii? eiiieaene, an? eiiieaene c N2O2-o?iiioi?ii oa aeaye? aioo??oiueieiiieaeni? iae?ioeeee?/i? niieoee c N4-o?iiioi?ii (CoL50, CoL62) ia ? EIE. sseui aeoiaeeoe c ?nioth/iai a e?oa?aoo?? i?eiouaiiy, ui eaoae?oe/i? aeanoeaino? oa?aeoa?i? eeoa aeey niieoe, a yeeo iiaeeeaee ?oo (-aeaeo?ii?a a iae?ie?eueoe? e?aaiaeo, oi EIE iiaeii? aooe an? aioeaiia? eiiieaene (CoL54, CoL61 ? CoL62). A oie aea /an, iayai?noue eaoae?oe/ieo aeanoeainoae a CoL51 (N-iiae?aia (-nenoaia) na?ae/eoue, ui ?ic?ea noi?yaeaiiy a iaeiiio i?noe? ia i?eaiaeeoue aei ao?aoe eaoae?oe/ieo aeanoeainoae. Iaeiae aaaaeaiiy aeaio ae?oaoe/ieo i?noe?a a iae?ioeeee ?aaeeeaeueii aieeaa? ia aeanoeaino? eiiieaeno - CoL50 ia ? EIE. A?aenooi?noue eaoae?oe/ieo aeanoeainoae o NiL62 aoea iiyniaia ii?ooaiiyi (-aeaeo?iiiiai noi?yaeaiiy aiane?aeie aeaoi?iaoe?e iae?ioeeeeo aeeeeeaieo noa?e/iei a?aeooiaooaaiiyi i?ioii?a iaoeeueieo a?oi ? a?iiaoe/ieo e?eaoeue. Iaeiae i?eioeeiiaei aeey iayaiino? o niieoee eaoae?oe/ieo aeanoeainoae ? oa, uia noi?yaeaieie caeeoaeinue ye i?i?ioi o?e oaeaoi? oeeeee, ye oea ia? i?noea a eiiieaenao NiL51 oa NiL54. I?eaaaeaia aeua aeiiaa aei aoaeiae EIE ? aii??e/iith ? ia a?aeiia?aea? ia ieoaiiy, ye? eiie?aoi? o?ceei-o?i?/i? oa?aeoa?enoeee eiiieaen?a aecia/athoue ?o eaoae?oe/i? aeanoeaino?. A??ia?aeii, na?aae ?ioeo aei ieo a?aeiinyoueny ? ca’ycai? c aoaeiaith e?aaiaeo ?aaeien-iioaioe?aee. I?i oea na?ae/aoue aeecuee? aiaeia?? a aeaeo?io?i?/i?e iiaaae?ioe? EIE NiL54 oa NiL61, aeey yeeo niinoa??aa?oueny ?yae iai?ioieo ?aaeien-ia?aoiae?a (aeea. aeua), a oie /an ye aeey NiL62 a?eueo?noue aeaeo?io?i?/ieo i?ioean?a iaiai?ioia. 3. Aieea aoaeiae eiiieaen?a ia iaoai?ci oa e?iaoe/i? iniaeeaino? ?aaeoe?e ieeniaiiy oao?aaiiaeueieo eiiieaen?a i?eaeth(??) oa i?ae?(??) 3.1. Aca?iiae?y iae?ioeeee?/ieo eiiieaen?a i?eaeth(??) c ia?ieniaeenoeueoaoii A yeino? ia’?eo?a aeine?aeaeaiiy aieeao aoaeiae ? noa?aio?i?/ieo oa?aeoa?enoee e?aaiae?a ia oaeaee?noue ieeniaiiy niieoe i?eaeth(??) aoee aea?ai? eiiieaene c iae?ioeeeeaie L1, L19-L29, L46 (5,7,7,12,14,14-aaenaiaoee-1,4,8,11-oao?aacaoeeeei-1,4,8,11-oao?a?i), L67 (5,12-aeeiaoee-5,7,12,14-oao?aaoee-1,4,8,11-oao?aacaoeeeeioao?aaeaea-7,1 4-ae??i), L68 ([15]aiN4) oa L69 ([9]aiN3). Aeine?aeaeaiiy i?iaiaeeee a ?ic/eiao 0,1 I H2SO4 aai 0,1 I HClO4, oaeaeeino? ?aaeoe?e a oiiaao iaaeeeoeo ieenieea aecia/aee ca ii/aoeiaeie e?i?eieie ae?eyieaie e?iaoe/ieo e?eaeo, caienaieo ia /anoio? oaee? iiaeeiaiiy NiIIIL. Ia?aa?a ieeniaiiy a?eueoino? eiiieaen?a NiIIL ia caeaaeeoue a?ae i?e?iaee eeneioe, ca aeiyoeii eiioi?ia??a L21 ? L23, aeey yeeo ?c-ca ianoaa?eueiino? a?aeiia?aeieo aeaaaaeoeo?a i?eaeth(???) niinoa??aathoueny neeaaei? e?iaoe/i? caeaaeiino? a HClO4. Aea/ai? ?aaeoe?? iathoue noao?iiao??th 2NiL2+ + S2O82- = 2 NiL3+ + 2 SO42- ? ?o oaeaee?noue i?aeei?y?oueny e?iaoe/iiio ??aiyiith v = d[NiIIIL]/dt = kniin [NiL2+] [S2O82-] (6) Aeey iieno oeeo i?ioean?a aoa cai?iiiiiaaiee ianooiiee iaoai?ci, oaeaee?nouee?i?ooth/ith noaae??th yeiai ? ieeniaiiy i?eaeth(??) a i?eaeue(???) (noaia 5), aea kniin = 2kox Kip. [NiL]2+ + S2O82- ( {[NiL]2+, S2O82-} (?iiia ia?a, Kip) (1) {[NiL]2+, S2O82-} ( [NiL]3+ + SO4- + SO42- kix (2) [NiL]2+ + SO4- ( [NiL]3+ + SO42- oaeaeeee i?ioean (3) Noaia 5 sse aeaeii c oaae. 13, aea i?eaaaeai? e?iaoe/i? ia?aiao?e aeine?aeaeaieo ?aaeoe?e, ae?aiacii ci?i kniin neeaaea? a?eueo i?ae 4 ii?yaeee, i?e oeueiio o?i?/ia i?e?iaea aeiii?ieo aoii?a ia a?a? i?eioeeiiai? ?ie?. Cia/ii a?eueo nooo?aeie ? i?inoi?ia? oa?aeoa?enoeee eiiieaen?a, a naia aeinooii?noue aen?aeueieo iieiaeaiue i?eaeth(??) aeey aoaee ?iiii S2O82-. sse na?ae/aoue e?oa?aoo?i? aeai?, iai?., a Ni??L20 oa (-Ni??L21 iaoeeuei? a?oie /anoeiai aeieothoue iaeaeaa aen?aeuei? iieiaeaiiy ? oe? eiiieaene oa?aeoa?ecothoueny aeecueeeie ? a?aeiinii iecueeeie aaee/eiaie kniin. A oie aea /an, a (-Ni??L21 oa (-Ni??L23 iaoeeuei? a?oie noai?ththoue ia?aoeiaee o?eueee c iaeiiai aieo ieiueie NiN4. sse iane?aeie, kniin aeey oeeo eiiieaen?a i?eaeecii ia aeaa ii?yaeee aeu? ? aeecuee? aei oaeeo aeey ieeniaiiy iacai?uaiiai Ni??L1. Aiaeia?/i? oaiaeaioe?? i?iyaeythoueny oaeiae ? i?e ieeniaii? Ni??L27 oa Ni??L28 - eiioi?iaoe?y (-Ni??L27 iiae?aia aei (-Ni??L21, a oie /an ye aoaeiaa (-Ni??L27 ? Ni??L28 iaaaaeo? aoaeiao Ni??L20. Oaaeeoey 13. Aoaeoeai? eiinoaioe oaeaeeino? (e/iieue n) oa aeoeaaoe?ei? ia?aiao?e ((I( a eAeae/iieue, (S( a Aeae/iieue E) ?aaeoe?e ieeniaiiy ia?ieniaeenoeueoaoii iae?ioeeee?/ieo eiiieaen?a i?eaeth(??) NiL a 0,1 I H2SO4 a) E?aaiae kniin (I( -(S( E?aaiae kniin (I( -(S( L1 15 (14) 39 (41) 109 (99) SYMBOL 97 \f "Symbol" -L24 1,1 57 48 L19 7,1 (6,1) 41 91 SYMBOL 98 \f "Symbol" -L24 1,8 44 95 L20 0,15 (0,12) 50 (54) 107 (97) L25 7,5 (6,4) 37 104 SYMBOL 97 \f "Symbol" -21 0,22 (a)) 64 57 L26 2,2 45 84 SYMBOL 98 \f "Symbol" -L21 20 (a)) 53 55 (-L27 1,5 (1,4) 52 78 SYMBOL 103 \f "Symbol" -L21 0,11 43 120 (-L27 0,08 (0,08) 64 48 SYMBOL 101 \f "Symbol" -L21 0,61 66 46 L28 0,007 - - L22 0,13 45 122 L67 2,6 (1,9) 51 78 SYMBOL 97 \f "Symbol" -L23 0,39 (a)) 60 65 L68 0,40 (0,36) 65 61 SYMBOL 98 \f "Symbol" -L23 19 (a)) 48 73 (L69)2 0,52 (0,52) 38 (37) 122(126) SYMBOL 103 \f "Symbol" -L23 0,12 43 132 - - - - I?ei?oee: a) - a aeoaeeao iaaaaeai? e?iaoe/i? ia?aiao?e ?aaeoe?e a 0,1 I HClO4; a) iaia ii/aoeiai? e?i?eii? ae?eyiee ia e?iaoe/i?e e?ea?e. Aei niia?eueiaiiy ?aaeoe?e i?eaiaeeoue oaeiae iayai?noue aen?aeueieo e?aaiae?a a eiiieaenao Ni??L. Iaea?eueo iai/ii aeaiee aoaeo i?iyaey?oueny i?e ieeniaii? eiiieaen?a, aeey yeeo iieiaeaiiy ??aiiaaae i?ae iecueeini?iiaith 4- oa aenieini?iiaith 6-eii?aeeiiaaieie oi?iaie caeaaeeoue a?ae ?I. Oae, i?io?e? caeaaeiino? kniin ieeniaiiy NiIIL2, NiIIL3 oa NiIIL8 a?ae ?I iathoue oi?io, iiae?aio aei caeaaeiino? a?ae ?I ai?noo 4-o eii?aeeiiaaii? oi?ie eiiieaen?a. A?aoiaoth/e oea, ??ai. (6) iiaeia caienaoe o aeaeyae? v=d[NiL3+]/dt ={[kin /(1+E??ai)] + [kan E??ai /(1+E??ai)]} [(NiL2+)]0 [S2O82-]0 (7) aea kniin=(kin + kan E??ai)/(1+E??ai), a kin oa kan - eiinoaioe oaeaeeino? ieeniaiiy a?aeiia?aeii iecueei- oa aenieini?iiai? oi?i eiiieaen?a i?eaeth(??). C aeaiiai ??aiyiiy aeo?ea?, ui aenieini?iia? eiiieaene aca?iiae?thoue c ia?ieniaeenoeueoaoii iaaaaaoi iia?euei?oa, i?ae iecueeini?iia?. Oaeee i?aeo?ae aeicaiey? iiynieoe a?aei?iiino? aeoeaaoe?eieo ia?aiao??a ?aaeoe?e ieeniaiiy Ni??L2, Ni??L3 ? Ni??L8 a 0,1 I H2SO4 a?ae Ni??L1 (oaae. 14). Oaaeeoey 14. E?iaoe/i? ia?aiao?e (kniin i?e 295 E a I-1 n-1, a aeoaeeao (I( a eAeae/iieue, (S( a Aeae/iieue E) ?aaeoe?e ieeniaiiy ia?ieniaeenoeueoaoii iiii- oa a?n(acaoeeeeaiiaeo) eiiieaen?a i?eaeth(??) Eiiieaen 0,1 I NaClO4 a) 0,1 I HClO4 0,1 I Na2SO4 a) 0,1 I H2SO4 NiL12+ 14,0 (39, -92) 14,0 (41, -99) 11,0 (37, -103) 15,0 (39, -109) NiL22+ 5,4 (a)) 4,0 (a)) 4,5 (39, -104) 0,92 (62, -52) NiL32+ 5,3 (41, -94) 3,7 (46, -77) 4,9 (45, -79) 0,86 (70, -22) NiL82+ 3,4 (42, -93) 2,2 (43, -91) 2,9 (44, -87) 0,22 (64, -42) Ni2L94+ - - 13,5 (43, -85) 12,3 (52, -45) Ni2L104+ - - 13,5 (42, -81) 13,0 (54, -39) Ni2L114+ - - 16.4 (43, -76) 7,8 (60, -21) Ni2L124+ - - 17,6 (44, -72) 4,4 (62, -24) I?ei?oee: a) pH 3,0); a) pH 3,3 aeey iiiiiae?ioeeee?/ieo oa ?I(6 aeey a?n(iae?ioeeee?/ieo eiiieaen?a; a) aeoeaaoe?ei? ia?aiao?e ia aecia/aeenue. Aeey ?aaeoe?e an?o eiiieaen?a a ia?oei?aoieo oa NiL12+ a noeueoaoai?nieo na?aaeiaeuao kniin ( kin , ine?eueee E??ai ( 1, ? aeoeaaoe?ei? ia?aiao?e ca’ycai? o?eueee c i?ioeanii ia?aiino aeaeo?iia. A oie aea /an, aeey acaoeeeeaiiaeo eiiieaen?a a 0,1 I H2SO4 E??ai (( 1, ? aeu? (I(ao ? (S(ao iiyniththoueny aeeaaeii a ieo oa?iiaeeiai?/ieo ia?aiao??a aeaii? ??aiiaaae. Caaaeii aiaeia?/iei /eiii iiaeia iiynieoe caeaaei?noue e?iaoe/ieo ia?aiao??a ieeniaiiy a?n(iae?ioeeee?/ieo) eiiieaen?a Ni??2L94+ - Ni??2L124+ (aeea. oaae. 14), oi/a a oeueiio aeiaaeeo iieiaeaiiy ni?iiai? ??aiiaaae a n??/aiieeneeo ?ic/eiao caeaaeeoue ye a?ae ?I, oae ? a?ae aeiaaeeie eaioethaa, ui ca’yco? iae?ioeeee?/i? noaiaeeieoe?. C iaoith a?eueo aeaoaeueiiai aiae?co i?e?iaee aeaiaioa?iiai aeoa ia?aiino aeaeo?iio a ?aaeoe?yo c S2O82- aoa aeei?enoaiee oi?iae?ci oai??? Ia?eona. Aeey iaeiiaeaeo?iiiiai ia?aoiaeo S2O82-+ a- ( S2O83- aoee acyo? e?oa?aoo?i? aaee/eie: Af =1,146 A a?aei. IEA oa eiinoaioa oaeaeeino? naiiiai?io k22(10-18 I-1 n-1. ?c-ca aeaioaeaeo?iiii? i?e?iaee S2O82- ye ieenieea a ?ic?aooieao aeei?enoaia eiinoaioa oaeaeeino? ieeniaiiy k12=0,5kniin, ?io? iicia/aiiy iathoue caaaeueiii?eeiyoee nain. Io?eiaia caeaaei?noue {ln(k12/f1/2)- lnW12} a?ae lnK12 aeey oei?iieeneeo ?ic/ei?a ? e?i?eiith (r=0,98, tg(=0,40(0,05), ui a?aeiia?aea? oai?aoe/i?e iiaeae?, iaeiae iathoue i?noea cia/i? (a?ae 3 aei 14 ii?yaee?a) a?aei?iiino? i?ae aaee/eiaie eiinoaio oaeaeeino? naiiiai?io aeaeo?iiii eiiieaen?a i?eaeth k11, io?eiaieie i?e aeaiiio i?aeoiae?, oa iaaaaeaieie a e?oa?aoo??. I?e/eiith oeueiai iiaea aooe iaei?aeoi?noue aeei?enoaiiy i?e ?ic?aooieo E12 cia/aiue Af ia?e NiIII/IIL aeey oei?iieeneeo ?ic/ei?a, ine?eueee i?iaeoeoaie ? noeueoaoi? aaeoeoe i?eaeth(III) (SO42- ooai?th?oueny a ?acoeueoao? a?aeiiaeaiiy S2O82-). Ca iiaaae?ieith a n??/aiieeneiio na?aaeiaeu? niieoee iiaeooue aooe ?icae?eai? ia e?eueea a?oi (?en.8). Aei ia?oi? a?aeiinyoueny eiiieaene iane/aieo ai?i?a, a yeeo iaeaeaa aen?aeuei? iiei- ?en. 8. Caeaaei?noue {ln(k12/f1/2) - lnW12} a?ae lnK12 aeey ?aaeoe?e ieeniaiiy eiiieaen?a NiIIL ia?ieniaeenoeueoaoii a n??/aiieeneeo ?ic/eiao (oeeo?e a?aeiia?aeathoue iiia?o e?aaiaeo). aeaiiy aeieiaai? iaoeeueieie cai?nieeaie (eaaae?aoe, r=0,95, tg(=0,63( 0,09). ?ic?aoiaai? cia/aiiy k11 aeey oeeo eiiieaen?a aeineoue aeecuee? aei iaaaaeaieo a e?oa?aoo??. Oea aeicaiey? i?eionoeoe ia?aaaaeii ciai?oiueinoa?iee (CN) iaoai?ci ia?aiino aeaeo?iia ia S2O82-. A??ia?aeii, ciaoiaeaeaiiy ia aeai?e i?yi?e oi/ie, ui a?aeiia?aeathoue noa?e/ii iaoo?oaeiaiei NiL1 oa NiL19, ? aeiaaeeiaei. Ae?oao a?oio neeaaeathoue eiiieaene ae??iiaeo iae?ioeeee?a (o?eeooieee, r=0,95, tg(=0,52( 0,06). Aeey ieo oa?aeoa?i? cia/ii aeu?, i?ae e?oa?aoo?i?, cia/aiiy k11, ui na?ae/eoue i?i ia?aa?a ?aaeoe?e ca aioo??oiueinoa?iei (AN) iaoai?ciii. A o?aoth a?oio (e?oaeee) aoiaeyoue niieoee, ianeiao?e/i? c oi/ee ci?o aeinooiiino? aen?aeueieo iieiaeaiue c iai?oaeaieie oaeaoieie oeeeeaie. A?aoiaoth/e i?ii?aeia iieiaeaiiy aeaieo eiiieaen?a, iiaeia i?eionoeoe, ui iaoai?ci ?o ieeniaiiy aeeth/a? ye CN, oae ? AN eiiiiiaioe. Aeey ci?i aeoeaaoe?eieo ia?aiao??a oa?aeoa?ia oaiaeaioe?y ca?eueoaiiy (I( c? ca?eueoaiiyi (S( (?en.9). An? eiiieaene iiaeia ?icae?eeoe ia aea? a?oie c e?i?eiith ei?aeyoe??th aeey eiaeii? (r=0,95 oa 0,87 aeey aa?oiuei? oa ieaeiuei? ?en. 9. Aca?iica’ycie i?ae aeoeaaoe?eieie ia?aiao?aie ?aaeoe?e ieeniaiiy eiiieaen?a i?eaeth(??) ia?ieniaeenoeueoaoii (oeeo?e a?aeiia?aeathoue iiia?o e?aaiaeo). i?yieo). Caaaeueieie ?enaie ia?oi? a?oie (eaa-ae?aoe) ? o?i?/ia iane/ai?noue aeiii?ieo aoii?a iae?ioeeee?a oa noa?e/ia ae?aioaaiiy aen?aeueieo iieiaeaiue i?eaeth(??). sse cacia/aeinue, naia aeey oeeo eiiieaen?a oa?aeoa?iee CN iaoai?ci ia?aiino aeaeo?iia. Ae?oaa a?oia eiiieaen?a (e?oaeee) ooai?aia ae??iiaeie e?aaiaeaie c iaea?eueo a??ia?aeiei AN ia?aiinii. Aei oe??? ae a?oie niieoe a?aeianai? eiiieaene NiL1, NiL19, (-NiL21 oa (-NiL23. A ieo, ia a?aei?io a?ae ai?iieo niieoe ia?oi? a?oie, aen?aeuei? iieiaeaiiy i?eaeth(??) aeinooii? aeey S2O82-. A??ia?aeii oea ?iaeoue iiaeeeaei AN iaoai?ci ia?aiino aeaeo?iia iaa?oue a oiio aeiaaeeo, eiee aeaaoi??aeueia ieiueia eii?aeeiaoe?eii? noa?e iaoaeo ooai?aia sp3-a?a?eaeeciaaieie aoiiaie acioo, ye? ia caeaoi? aei (-aeaoeaii? aca?iiae?? c ?iiii iaoaeo. 3.2. E?iaoe/i? iniaeeaino? ?aaeoe?e ieeniaiiy ai?aeai?nieo eiiieaen?a i?ae?(??) oa i?eaeth(??) ia?ieniaeenoeueoaoii sse ? aeey ai?iieo nenoai, aca?iiae?y S2O82- c ai?aeieie eiiieaenaie i?eaeth(??) aai i?ae?(??) noi?iaiaeaeo?oueny ooai?aiiyi niieoe iaoae?a(???) ? i?aeei?y?oueny e?iaoe/iiio ??aiyiith (6). Io?eiai? e?iaoe/i? ia?aiao?e aeine?aeaeaieo i?ioean?a i?eaaaeai? a oaae. 15. No?oeoo?iith iniaeea?noth 4-eii?aeeiiaaieo ai?aeieo eiiieaen?a i?eaeth(??) ? oa, ui aeaaoi??aeueiee e?aaiae ia noai?th? noa?e/ieo ia?aoeiae aeey aen?aeueii? aca?iiae?? c ieenieeii, oiae? ye a eiiieaenao i?ae?(??) aen?aeuei? iieiaeaiiy caeiyo? iieaeoeaie aiaee. Iaenooo?a?oith a?aei?ii?noth iiaaae?iee eiiieaen?a i?eaeth a?ae i?ae? ? cia/ii aeua (a?ae 10 aei 2000 ?ac) oaeaee?noue ?o ieeniaiiy. Oeae aoaeo iiynith?oueny aeoaea iecueeeie cia/aiiyie (H(, ye? a?eueo i?ae eiiiainothoue iani?eyoeeaee aeeaae (S(. I?e oeueiio na?aae eiiieaen?a eiaeiiai c iaoae?a a?aei?iiino? a eiinoaioao oaeaeeino? oaeiae aa??ththoueny a aeineoue oe?ieeo iaaeao (a?eueo i?ae a 50 ?ac?a). Aiae?c e?iaoe/ieo aeaieo c canoinoaaiiyi ??aiyiiy Ia?eona na?ae/eoue, ui ?ic?aoiaai? eiinoaioe k11 aeey a?eueoino? niieoe i?ae? aeecuee? aei aaee/ei, ui oa?aeoa?ecothoue iaioeaei? eiiieaene. Oea neoaeeoue aaaiiei a?aoiaioii ia ei?enoue CN (aai aeecueeiai aei iueiai) iaoai?cio ia?aiino aeaeo?iia c i?ae?(??) ia S2O82-. A oie aea /an, ?ic?aoiaai? aaee/eie k11 aeey eiiieaen?a i?eaeth a aaaaoueio aeiaaeeao ? iaaecae/aeii aenieeie. Oaea niaoeeo?ea na?ae/eoue i?i AN iaoai?ci i?ioean?a ca o/anoth aeaieo niieoe, oiaoi aeicaiey? noaa?aeaeoaaoe, ui ieeniaiiy eiiieaen?a i?eaeth(??) oa i?ae?(??) a?aeaoaa?oueny ca ??cieie iaoai?ciaie. sse ? aeey ai?iieo niieoe, aeey ai?aeieo eiiieaen?a iaio iaoae?a oa?aeoa?ia aeecueea aei e?i?eii? caeaaei?noue i?ae aeoeaaoe?eieie ia?aiao?aie (?en.10). A?aoiaoth/e a?aei?iiino? a iaoai?ci? ieeniaiiy oeeo ?ii?a, neiioiiaoe/iei ? oaeo, ui aca?iia ?ici?uaiiy i?yieo ia ?en.10 aeoaea iaaaaeo? iieacaia ia ?en.9 - a iiia?aaeiueiio aeiaaeeo i?yia, ui ca’ycoaaea aeoeaaoe?ei? ia?aiao?e CN ia?aiino aeaeo?iia, oaeiae aoea ?icoaoiaaia aeua, i?ae aiaeia?/ia i?yia aeey AN ?aaeien-i?ioean?a. Oaaeeoey 15. E?iaoe/i? ia?aiao?e (kniin a e/iieue n, (H( a eAeae/iieue, (S( a Aeae/iieue E) ?aaeoe?e ieeniaiiy MIIL ia?ieniaeenoeueoaoii (298 E, 0,1 iieue/e NaClO4) ?en. 10. Aca?iica’ycie i?ae aeoeaaoe?eieie ia?aiao?aie ?aaeoe?e ieeniaiiy ai?aeieo eiiieaen?a i?eaeth(??) (() oa i?ae?(??) (() ia?ieniaeenoeueoaoii (oeeo?e a?aeiia?aeathoue iiia?o e?aaiaeo). Io?eiai? ?acoeueoaoe aeicaieeee i?eionoeoe, ui a yeino? ieeniee?a NiIIL iiaeooue aenooiaoe ? ?io? ia?ieneaee, iai?., oae?, ui ooai?ththoueny i?e caa??aaii? i?aai?/ieo ?a/iaei a aa?iaieo oiiaao. Aeey c’ynoaaiiy oeueiai aoea aeine?aeaeaia iiaaae?iea NiIIL1, NiIIL20, NiIIL22, NiIIL25, NiIIL27, NiIIL30 ? NiIIL33 a ?aaeoe?yo c ia?ieneeueieie ?aaeeeaeaie aeeiaoeenoeueoieneaeo (AeINI) ye iiaeaeueiiai ieenieea. Aoei anoaiiaeaii, ui aeai? eiiieaene niia?eueiththoue aca?iiae?th AeINI c I2, oiaoi ? ?ia?a?oi?aie aaoiieeniaiiy, i?e oeueiio nooi?iue ieeniaiiy iaoaeo ia ? i?eioeeiiaith - Ni??L1 oa N???L1 iathoue iiae?ai? aeanoeaino?, ye? iaa?oue ia?aaeuothoue oa?aeoa?enoeee i?iieneiaeo ?ia?a?oi??a. 3.3. Aca?iiae?y iae?ioeeee?/ieo eiiieaen?a i?eaeth c a?iiaoii a yeino? ?ioiai ieenieea aeey NiIIL aoa aeei?enoaiee oaeiae a?iiao, ine?eueee a?i ? eeth/iaei ?aaaaioii a eieeaaeueieo o?i?/ieo ?aaeoe?yo, a yeeo, ye aoei aeyaeaii iaie, i?eeiathoue o/anoue aeaye? iae?ioeeee?/i? eiiieaene i?eaeth (aeea. ieae/a). sse ia’?eoe aea/aiiy aoee aea?ai? Ni??L1, Ni??L19, Ni??L20, (-,(-, (- ? (-Ni??L21, Ni??L22, (-, (- ? (-Ni??L23, (- ? (-Ni??L24, Ni??L25, (- ? (-Ni??L27, Ni??L28, Ni??L29 ? Ni??L46. I?iaaaeai? aeine?aeaeaiiy iieacaee, ui i?ioean ieeniaiiy a 0,1 I H2SO4 i?eaiaeeoue aei ooai?aiiy eiiieaen?a [NiIIIL(SO4)n(H2O)2-n](3-2n)+ (aea n=1 aai 2). Ca iniaeeainoyie ia?aa?ao ?aaeoe?e ieeniaiiy niieoee iiaeia ?icae?eeoe ia aea? a?oie. Aei ia?oi? a?aeiinyoueny eiiieaene c L1, L19, L24 oa L25, oaeaee?noue ieeniaiiy yeeo iieno?oueny ??ai. (8) (aaee/eie kniin i?eaaaeai? a oaae. 16). Aeaeyae e?iaoe/ieo e?eaeo ?aaeoe?e ieeniaiiy eiiieaen?a ae?oai? a?oie na?ae/eoue i?i ?o ia?aa?a a aaoieaoae?oe/iiio ?aaeei?. Iaeneiaeueia oaeaee?noue ieeniaiiy iieno?oueny ??aiyiiyi, aiaeia?/iei (8), c cai?iith kniin ia kiaen (aeea. oaae.16) v = d[Ni???L]/dt = kniin [Ni??L] [KBrO3] [H2SO4] (8) Oaaeeoey 16. Eiinoaioe oaeaeeino? (I-2 n-2) ieeniaiiy a?iiaoii iae?ioeeee?/ieo eiiieaen?a i?eaeth(??) NiL2+ a n??/aiieeneeo ?ic/eiao (295 E) L kniin Af, iA a?aei. IAA L kiaen Af, iA a?aei. IAA L1 11 780 L20 27 940 oa 1110 L19 4,5 800 SYMBOL 97 \f "Symbol" -L21 6,9 1075 (-L24 0,069 ia aei??thaaany SYMBOL 98 \f "Symbol" -L21 6,5 iaiai?. SYMBOL 98 \f "Symbol" -L24 0,12 990 L28 1,6 iaiai?. L25 0,30 965 Iaiao?aeii cacia/eoe, ui a ?aaeoe?yo c a?iiaoii noa?aio?i?/i? oa?aeoa?enoeee eiiieaen?a a?ae?a?athoue cia/ii iaioo ?ieue. A oeueiio aeiaaeeo iayai?noue aai a?aenooi?noue aaoieaoae?co acaaae? ia ei?aeth? c o?i?/iith /e i?inoi?iaith aoaeiaith niieoe. Iniiaiei oaeoi?ii, yeee, ia iaoo aeoieo, aecia/a? a?aei?iiino? a o?i?/i?e iiaaae?ioe? eiiieaen?a, ? iioaioe?ae ia?e Ni???/??L - aeey niieoe ia?oi? a?oie Ef iaio iiceoeai?, i?ae aeey ae?oai?, i?e oeueiio aaee/eia kniin ciaioo?oueny c ?inoii Af. Oae? ae oaiaeaioe?? oa?aeoa?i? ? aeey ?aaeoe?e eiiieaen?a ae?oai? a?oie - Ni??L20 oa Ni??L22 (ye? iathoue iaeieae/? iioaioe?aee na?aae aeaieo niieoe) aei ii/aoeo aaoieaoae?oe/ii? noaae?? ieeniththoueny, oi/a ? a?aeiinii iia?eueii, a?iiaoii aei i?eaeth(???), oiae? ye aeey ?ioeo eiiieaen?a oaeee aoaeo ia niinoa??aa?oueny. Aiae?c iiaeeeaiai iaoai?cio i?ioean?a aeicaiey? c?iaeoe aeniiaie, ui iaea?eueo a??ia?aeiei ieenieeii eiiieaen?a ia?oi? a?oie ? aeania a?iiao-?ii NiL2+ + BrO3- + 2H+ ( NiL3+ + BrO2( + H2O (9) NiL2+ + BrO2( + H+ ( NiL3+ + IBrO2 (10) A?aoiaoth/e, ui ?aaeien-iioaioe?ae ia?e BrO3-/BrO2( aei??aith? 1,15 A a?aei. IAA, iiaeia i?eionoeoe, ui aeey eiiieaen?a ae?oai? a?oie ?aaeoe?y (9) ia aoaea a?aoe nooo?ai? ?ie? aiane?aeie oa?iiaeeiai?/ieo i?e/ei. A oeueiio aeiaaeeo ieeniaiiy eaea aaoieaoae?oe/iei oeyoii, i?e/iio ?ioa?iaae?aoii, yeee aeeth/a? aaoieaoae?oe/io noaae?th, ? IBrO2 (IBrO2 + BrO3- + H+ ( 2BrO2(+ I2O). A?ii?euei? ?aaeeeaee ieeniththoue NiIIL, a?aeiiaethth/enue aei IBrO2 (??ai. (10)), ui ? i?eaiaeeoue aei aaoieaoae?co. 3.4. Eieeaaeuei? o?i?/i? ?aaeoe?? (EO?) ca o/anoth iae?ioeeee?/ieo eiiieaen?a i?eaeth Aeine?aeaeaiiy ?aaeien-iiaaae?iee eiiieaen?a i?eaeth aeicaieeee cia/ii ?icoe?eoe eiei niieoe, caeaoieo aenooiaoe ye eaoae?caoi?e, aai iaeii/anii ye eaoae?caoi?e ? noano?aoe a EO? ca o/anoth a?iiaoo. Iaea?eueo aeaoaeueii aoea aea/aia iiaaae?iea a EO? eiiieaeno NiL28, ?io? eiiieaene a iniiaiiio aaaeooue naaa aiaeia?/iei /eiii. A ?aaeoe?? BrO3- c iaeiiiaith eeneioith (MK) ye noano?aoii a i?enooiino? Ni??L28 ?a?no?othoueny ia??iaee/i? ci?ie iioaioe?ae?a Br--naeaeoeaiiai oa ieaoeiiaiai aeaeo?iae?a. Ia?aeaeueii c oeei a?aeaoaa?oueny aca?iiia?aoai?aiiy Ni??L28 ( Ni???L28. Oi?ia, aiie?ooaea ia??iae eieeaaiue, iiyaa neeaaeieo ?aaeei?a oeio LSn i?e ?ioeo iino?eieo oiiaao aeoaea caeaaeeoue a?ae eiioeaio?aoe?e ?aaaaio?a. *enei eieeaaiue aeineoue cia/ia: i?e ii/aoeiaeo eiioeaio?aoe?yo (I) [KBrO3]=0,10, [MK]=0,12, [H2SO4]=0.60 oa [NiL282+]=0,01 ia i?ioyc? 1,5 aiae niinoa??aa?oueny a?ey 60 eieeaaiue. A i?ioean? EO? a?aeaoaa?oueny, a??ia?aeii, iiaia ieeniaiiy a?iiaoii i?aai?/ii? /anoeie iae?ioeeee?/iiai eiiieaeno i?eaeth, ui aoei i?aeoaa?aeaeaii oeyoii ian-niaeo?iiao?e/iiai aiae?co i?iaeoeo?a. A?aeiii, ui aeey aeieeiaiiy oa ?nioaaiiy EO? iaiao?aeia cae?eniaiiy iecee oiia, na?aae yeeo i?eioeeiiaeie ? iae?i?eiee ia?aa?a i?ioean?a oa iayai?noue cai?ioieo ca’yce?a. Aeua a?aei?/aeinue, ui aoaeiaa eiiieaeno aieeaa? ia o?eueee ia oaeaee?noue eiai ieeniaiiy a?iiaoii, aea ? ia nai iaoai?ci i?ioeano (iayai?noue aaoieaoae?oe/ii? noaae??). Ia iaio i?eioeeiiaith aeey ?aae?caoe?? EO? ? oaeaee?noue aioo??oiueieiiieaeniiai a?aeiiaeaiiy NiIIIL. sse aeieeaa? c io?eiaieo aeaieo, iaiao?aeiith oiiaith o/ano? eiiieaeno a EO? aac noano?aoo ? iayai?noue aaoieaoae?oe/ii? noaae?? eiai ieeniaiiy a?iiaoii. Iaeiae oey oiiaa ia ? aeinoaoiueith - eiiieaene Ni??L20 oa Ni??L22, ieeniaiiy yeeo i?io?ea? aaoieaoae?oe/iei oeyoii, ia i?eeiathoue o/ano? a EO? aac IE. A??ia?aeii, ae?oaith iaiao?aeiith oiiaith ? caeaoi?noue i?eaeth(???) a?aeiinii oaeaeei a?aeiiaethaaoenue ca ?aooiie ieeniaiiy iae?ioeeeeo. Caaaeii, iaie aoee ciaeaeai? EO? a nenoaiao BrO3- - Ni??L - H2SO4 aeey an?o niieoe i?eaeth, ye? ieeniththoueny a?iiaoii a aaoieaoae?oe/iiio ?aaeei?, i?e oiia?, ui k?icee a?aeiia?aeiiai eiiieaeno Ni???L (10-4 n-1. Io?eiai? ?acoeueoaoe aeicaieythoue oaeiae iiynieoe a?aei?ii?noue a iiaaae?ioe? aeaio N-?ciia?ieo eiiieaen?a - Ni??L20 c iaeiiai aieo, oa N-eiioi?ia??a Ni??L21 c ?ioiai. Ia?oee c ieo ieenith?oueny a?iiaoii a eieeaaeueiiio ?aaeei? o?eueee a i?enooiino? IE, oiae? ye ae?oa? i?eeiathoue o/anoue a EO? iaio oei?a. A??ia?aeii, ?aaeoe?y eiiieaeno Ni???L20 c a?aeiiaieeii (IE) i?eaiaeeoue aei i?aeaeuaiiy oaeaeeino? ?aaaia?aoe?? Ni??L20 ? o?eueee oiae? aeinyaa?oueny iaiao?aeia aeey ia?aa?ao eieeaaeueieo i?ioean?a ni?aa?aeiioaiiy oaeaeeinoae ?aaeoe?e a nenoai?. AENIIAEE 1. Aiae?c e?oa?aoo?ieo aeaieo cana?ae/ea, ui ieoaiiy i?i oeyoe oi?aae?iiy ?aaeien-oa?aeoa?enoeeaie eii?aeeiaoe?eieo niieoe e??i /enoi ooiaeaiaioaeueiiai aniaeoo, ui iieyaa? o anoaiiaeaii? aca?iica’yceo i?ae aoaeiaith eii?aeeiaoe?eiiai iie?aae?o ? aeanoeain oyie eiiieaeno, ? aeooaeueiei ? c i?eeeaaeii? oi/ee ci?o, ine?eueee eiiieaene iaoae?a a ci?iieo nooiaiyo ieeniaiiy ? eaoae?caoi?aie aaaaoueio i?ioean?a, aeeth/ath/e oioi- oa aeaeo?io?i?/i? ?aaeoe??, aenooiathoue ye naeaeoeai? ?aaaaioe oiui. Oiio iaoith aeaii? ?iaioe aoei anoaiiaeaiiy aca?iica’yceo i?ae aoaeiaith eiiieaen?a iaoae?a c acioai?nieie e?aaiaeaie ? iniaeeainoyie oa?iiaeeiai?/iiai oa e?iaoe/iiai aniaeo?a ?o ?aaeien-iiaaae?iee, a oaeiae iiooe oeyo?a noaa?e?caoe?? iao?aaeeoe?eieo nooiai?a ieeniaiiy iaoae?a. 2. A ?iaio? cai?iiiiiaai? i?ea?iaeuei? iaoiaee neioaco, ca aeiiiiiaith yeeo io?eiai? aeecueei 50 iiaeo eii?aeeiaoe?eieo niieoe i?eaeth(??) oa i?ae?(??), a naia: eiiieaene oao?aaeaioaoieo iaioa- ? aaenaaca- iae?ioeeee?a, ui i?noyoue iaeii?aeeiiaai? aoiie acioo c iaiaeaioieie cai?nieeaie; eiiieaene a?aee?eoieaioethaiaeo oa iae?ioeeee?/ieo ae?ai?aeiae?ai?iieo e?aaiae?a, ui a?ae??ciythoueny ?ici??ii oaeaoieo oeeee?a oa a?aeiiniei iieiaeaiiyi ea?aii?eueieo a?oi; a?n(iae?ioeeee?/i?) eiiieaene ia iniia? 14-/eaiieo noaiaeeieoeue c? ca’ycoth/ei i?noeii ci?iii? aeiaaeeie. Ii?yae c oeei, a ?iaio? aoee oaeiae aea/ai? ?aaeien-aeanoeaino? ?yaeo iienaieo ?ai?oa niieoe, aei yeeo a?aeiinyoueny: eiiieaene i?eaeth(??) oa eiaaeueoo(???) c iaeo?aeueieie 14-/eaiieie oao?aacaiae?ioeeeeaie ??ciiai nooiaiy cai?uaiino? oa/aai iaiane/aiino?; eiiieaene aee?eeiaaeueoo(???) c ae?ai?iiieie iae?ioeeee?/ieie N4- aai iaoeeee?/ieie N2O2-e?aaiaeaie oa iae?ia?oeeee?/i? eiiieaene eiaaeueoo(???). 3. Anoaiiaeaii, ui iniiaiei /eiieeii, yeee aecia/a? aaee/eie ?aaeien-iioaioe?ae?a ia? NiIII/IIL ? CuIII/IIL a oao?aaiiaeueieo eiiieaenao, ? aoaeiaa aeaaoi??aeueiiai e?aaiaeo (i?e?iaea aeiii?ieo aoii?a, ?ici?? iae?ie?eueoey, ?ici?? oa aca?iia ?ici?uaiiy oaeaoieo oeeee?a, i?e?iaea oa i?inoi?iaa iai?aaeai?noue cai?niee?a). I?e oeueiio aieea eiie?aoiiai oaeoi?a ia iaia’yceiai ? iaeiaeiaei aeey i?eaeth oa i?ae?, a aecia/a?oueny neiao???th i?a?oaeae, ui ci?iththoue naith canaeai?noue a ?acoeueoao? ?aaeien-ia?aoiaeo, oa aoaeiaith eii?aeeiaoe?eieo iie?aae??a ?ii?a, ui neeaaeathoue ?aaeien-ia?o. Iieacaii, ui i?eioeeiiaa cia/aiiy aeey oa?iiaeeiai?/ii? noaa?e?caoe?? iaoae?a(???) (iiieaeaiiy ?aaeien-iioaioe?aeo ia?e MIII/IIL) ia? i?inoi?iaa aoaeiaa aeaaoi??aeueieo e?aaiae?a, ?o no?oeoo?ia aei?noe?noue ? caeaoi?noue caaeiaieueiyoe noa?aio?i?/i? aeiiae i?eaeth(???) oa i?ae?(???). I?e oeueiio ?aaeien-oa?aeoa?enoeee eiiieaen?a c a?aee?eoieaioethaiaeie e?aaiaeaie ianooo?ai a?ae??ciythoueny a?ae oaeeo aeey iae?ioeeee?/ieo niieoe c aiaeia?/iei iaai?ii aeiii?ieo aoii?a. Ia iniia? io?eiaieo ?acoeueoao?a cai?iiiiiaai? niiniae oi?aae?iiy ?aaeien-iioaioe?aeaie ia? NiIII/IIL ? CuIII/IIL a oe?ieiio ae?aiacii? oeyoii ci?ie i?e?iaee aeiii?ieo aoii?a e?aaiae?a, cai?niee?a a iae?ioeeeeao aai neeaaeo na?aaeiaeua. 4. Ia i?eeeaae? aeaio oei?a ?aaeoe?e, ye? iathoue i?noea o aioo??oi?e eii?aeeiaoe?ei?e noa?? eiiieaen?a eiaaeueoo, i?eaeth ? i?ae?, anoaiiaeai? caaaeuei? caeiiii??iino? ?aaeien-i?ioean?a a?aeiiaeaiiy iaoae?a(???) aei iaoae?a(??) ca ?aooiie ieeniaiiy aeaaoi??aeueiiai e?aaiaeo aai aiiie?oe/iiai ?ic?eao ca’yceo iaoae(???) - aen?aeueiee e?aaiae: Iieacaii, ui e?iaoe/ia noaa?euei?noue eii?aeeiaoe?eieo niieoe i?eaeth(???) oa i?ae?(???) a oao?aaca ioi/aii? o?eueee a caaaeueiiio aeiaaeeo ciaioo?oueny neiaaoii i?aeaeuaiith ?aaeien-iioaioe?aeo ia?e IIII/IIL. ?nio? iecea oaeoi??a (noa?aio?i?/i? ? aeaeo?iii? oa?aeoa?enoeee e?aaiae?a, nooi?iue ?o i?ioiioaaiiy, iayai?noue o ?ic/ei? aeiaeaoeiaeo ai?ii?a), ye? aieeaathoue ia oaeaee?noue ?iceeaaeo ieeniaieo oi?i eiiieaen?a. Ciaeaeai? caeiiii??iino? aeicaieeee cai?iiiioaaoe niiniae io?eiaiiy e?iaoe/ii noaa?eueieo niieoe, ui oa?aeoa?ecothoueny aenieeie aeiaeaoieie ?aaeien-iioaioe?aeaie; C’yniaaiee aieea aoaeiae aeaaoi??aeueieo e?aaiae?a a 5-eii?aeeiiaaieo eiiieaenao i?aaiieiaaeueoo(???) ia e?iaoe/i? oa?aeoa?enoeee ? eaaioia? aeoiaee ?aaeoe?e aiiie?oe/iiai ?ic?eao ca’yceo eiaaeueo-aoaeaoeue. Oeae aieea i?i?ioa?i?aoiaaiee a oa?i?iao a) ?aaeien-iioaioe?ae?a niieoe; a) aioo??oiueiiieaeoey?iiai ia?a?iciiae?eo aeaeo?iiii? aonoeie a caeaaeiino? a?ae oeio aeaaoi??aeueiiai e?aaiaeo, oa a) o?i?/ieo aeanoeainoae ?ic/eiieea; Iieacaii, ui aoaeoeai?noue i?ioeano aiiie?oe/iiai ?ic?eao ca’yceo eiaaeueo - aaeiaai?ae (eaaioiaee aeo?ae oioia?aeiiaeaiiy eiaaeueoo(???) a aeeaaeiaai?aeieo eiiieaenao c iae?ioeeee?/ieie oao?aai?iaie) iaei caeaaeeoue a?ae aoaeiae aeaaoi??aeueiiai iae?ioeeeeo ? aecia/a?oueny aeaeo?iiieie aeanoeainoyie aen?aeueieo e?aaiae?a oa ?aaeoe?eiith caeaoi?noth ooai?aieo a ?acoeueoao? ia?aiino aeaeo?iia ?aaeeeae?a a ?aaeoe?yo ?o ?iceeaaeo aai aca?iiae?? c eiiiiiaioaie na?aaeiaeua. 5. Anoaiiaeai? e?iaoe/i? iniaeeaino? ?aaeoe?e ieeniaiiy oe?ieiai iaai?o ai?iieo eiiieaen?a i?eaeth(??) ? i?ae?(??) i?ae ae??th ieeniee?a ??cii? i?e?iaee. Iieacaii, ui ieeniaiiy eiiieaen?a i?eaeth(??) a?iiao-?iiaie a caeaaeiino? a?ae aoaeiae aeaaoi??aeueiiai e?aaiaeo a?aeaoaa?oueny aai iaeaoae?oe/iei oeyoii, aai ? aaoieaoae?oe/iei. Aeey ?aaeoe?e oeueiai oeio iinooeueiaaiee ciai?oiueinoa?iee iaoai?ci ia?aiino aeaeo?iia, a a?aei?iiino? a iiaaae?ioe? niieoe i?i?ioa?i?aoiaai? c caeo/aiiyi aeaieo i?i aaee/eie ?aaeien-iioaioe?ae?a ?aaaaio?a. 6. Iieacaii, ui ia i?ioeaaao aeuacaaaeaiei ?aaeoe?yi ieeniaiiy iae?ioeeee?/ieo eiiieaen?a i?eaeth(??) ia?ieniaeenoeueoao-?iiaie a?aeaoaa?oueny ca iaeiaeiaei o?i?/iei iaoai?ciii, i?e oeueiio i?e?iaea aeaiaioa?iiai aeoo ia?aiino aeaeo?iia aecia/a?oueny i?inoi?iaith aoaeiaith a?aeiiaieea ? i?e?iaeith aeiii?ieo aoii?a e?aaiaeo. O aeiaaeeo noa?e/ii ae?aiiaaieo eiiieaen?a i?ioeane iiaeia o?aeooaaoe ye ciai?oiueinoa?iee ia?aiin aeaeo?iia, oiae? ye a?aenooi?noue aen?aeueiiai aeieoaaiiy a eii?aeeiaoe?ei?e noa?? iaoaeo oa/aai aaaaeaiiy a e?aaiae aciiaoeiiaeo aeiii?ieo a?oi i?eaiaeeoue aei i?aeaeuaiiy aeeaaeo aioo??oiueinoa?iiai oeyoo. C a?aooaaiiyi oeueiai i?i?ioa?i?aoiaai? aeoeaaoe?ei? ia?aiao?e aea/aieo i?ioean?a ? iieacaia canoiniai?noue oai??? Ia?eona aei iieno ?aaeoe?e, ye? noi?iaiaeaeothoueny ?ic?eaii o?i?/iiai ca’yceo. 7. Aaeaeaaoi?noue cai?iiiiiaaiiai i?aeoiaeo i?aeoaa?aeaeaia aeine?aeaeaiiyi e?iaoe/ieo iniaeeainoae ?aaeoe?e ieeniaiiy ia?ieniaeenoeueoaoii iiii- ? a?n(iae?ioeeee?/ieo) eiiieaen?a i?eaeth(??), aeey yeeo ??aiiaaaa i?ae 4- oa 6-eii?aeeiiaaieie oi?iaie caeaaeeoue a?ae ?I, a oaeiae eiiieaen?a i?eaeth(??) oa i?ae?(??) c ae?ienioao?aai?iaie. Io?eiai? aeey inoaiiueiai oeio niieoe aaee/eie eiinoaio oaeaeeino? naiiiai?io aeaeo?iiii a ia?ao IIIIL/IIIL i?aeoaa?aeaeothoue aioo??oiueinoa?iee i?ioean ieeniaiiy eaaae?aoii-ieaia?ieo eiiieaen?a i?eaeth(??) oa ciai?oiueinoa?iee iaoai?ci ieeniaiiy oanoeeii?aeeiiaaieo niieoe i?ae?(??). 8. Aea/aiiy oa?iiaeeiai?/ieo aeanoeainoae oa e?iaoe/ieo oa?aeoa?enoee ?aaeoe?e ?aaeien-ia? IIII/IIL aeicaieeei ciaeoe iaa?aeii? ?ai?oa i?ioeane aaoieaoae?oe/iiai aiiie?co ca’yceo eiaaeueo-aoaeaoeue a aaeiaaiai?nieo ?ic/eiieeao oa eieeaaeuei? o?i?/i? ?aaeoe?? ca o/anoth iae?ioeeee?/ieo eiiieaen?a i?eaeth(??,???) ? iiynieoe ?o iaoai?cie. 9. Iieacaia ia?niaeoeai?noue aeei?enoaiiy aeayeeo c aeine?aeaeaieo niieoe a i?ioeanao, ui iiaeooue ciaeoe i?aeoe/ia canoinoaaiiy: acaiae?ioeeee?/ieo eiiieaen?a eiaaeueoo ye eaoae?caoi??a oioi?i?oe?eiaaiiai ieeniaiiy nie?o?a iieaeoey?iei eeniai; oao?aacaaioeaiiaeo eiiieaen?a eiaaeueoo ye eaoae?caoi??a ia?aaea/? eaioethaa c iie?ia?o ia iiiiia? a ?aaeeeaeuei?e iie?ia?ecaoe?? ae?eeiaeo iiiiia??a; eii?aeeiaoe?eieo niieoe i?eaeth(??) oa i?eaeth(???) c iae?ioeeee?/ieie oa a?aee?eoieaioethaiaeie e?aaiaeaie ye ?ia?a?oi??a i?ioean?a ?aaeeeaeueiiai ieeniaiiy i?aai?/ieo niieoe eeniai. 10. Oaeei /eiii, a aeai?e ?iaio? ia iniia? nenoaiaoecaoe?? ?nioth/eo aeaieo, oe?eani?yiiaaiiai neioaco iiaeo eii?aeeiaoe?eieo niieoe oa i?iaaaeaiiy ??ciiiai?oieo aenia?eiaioaeueieo aeine?aeaeaiue c’yniaaiee aieea aoaeiae niieoe ia ieenithaaeueii-a?aeiiaethaaeueieie iioaioe?aee ? e?iaoe/i? ia?aiao?e ?aaeien-?aaeoe?e ca o/anoth eiiieaen?a eiaaeueoo(???,??), i?eaeth(???,??) oa i?ae?(???,??), ui aeicaiey? oeyoii ci?ie aoaeiae eii?aeeiaoe?eieo iie?aae??a ?ii?a iaoae?a cae?enithaaoe oi?aae?iiy oa?iiaeeiai?/ieie oa?aeoa?enoeeaie ia? iaoae(???/??), e?iaoe/iith noaa?euei?noth eiiieaen?a iaoae?a(???) ? ?aaeoe?eiith caeaoi?noth eii?aeeiaoe?eieo niieoe a i?ioeanao, ye? noi?iaiaeaeothoueny ci?iith nooiaiy ieeniaiiy iaoaeo. Iniiaiee ci?no ?iaioe aeeeaaeaiee a ioae?eaoe?yo: ssoeeie?neee E.A., Eaiiaea ss.Ae. Oeceeioeiey eiiieaenia iaoaeeia n iae?ioeeeee/aneeie eeaaiaeaie.- Eeaa: Iaoeiaa aeoiea, 1985.- 356 n. ssoeeie?neee E.A., Eaiiaea ss.Ae. 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Aaa?eo N.I., Eaiiaea ss.Ae. No?iaiea eeaaiaeia e ?aaeien iioaioeeae ia?u Ni(III)/Ni(II) a aaenaaca ie?oaeaiee / AEo?i. iai?aai. oeiee.- 1996.-O.41, N8.- N.1311-1314. Maeiooai E.M., Eaiiaea ss.Ae. (2-Aeae?ieneyoee)caiauaiiua acaiae?ioeeeee/aneea eiiieaene iaaee(II) - neioac e naienoaa / AEo?i. iai?aai. oeiee.- 1996.- O.41, N11.- N.1845-1850. Padlock macrocyclic complexes. The synthesis of a range of nickel(II) complexes of N-alkyl azacyclams and the crystal structure of (3-ethyl-1,3,5,8,12-pentaazacyclotetradecane) nickel(II) perchlorate / R.W.Hay, A.Danby, P.Lightfoot, Ya.D.Lampeka // Polyhedron.- 1997.- V.16, N16.- P.2777-2783. Aaa?eo N.I., Eaiiaea ss.Ae. Aeeyiea i?ioiie?iaaiey aieaeiie a?oiiu ia niaeo?aeueiua e ieeneeoaeueii-ainnoaiiaeoaeueiua oa?aeoa?enoeee eiiieaenia ieeaey e iaaee n iiiiienioeeeeaiii // AEo?i. iai?aai. oeiee.- 1997.- O.42, N5.- N.742-748. Niinia ii?aaeaeaiey ?anoai?aiiiai a aiaea eenei?iaea / E.A.ssoeeie?neee, TH.E. A?aoooei, E.E.Caoeiu, ss.Ae.Eaiiaea // Aao. naeaeao. NNN? ?821404 ii cayaea ?2676900 io 11.10.78 a., ca?aa. 12.12.80 a., iioae. 15.04.81 a. Athee. N14. I.Ee.3 N 01 A 13/00, G 01 N 21/27. Niee 2,3,9,10-oao?aiaoee-1,4,5,7,8,11,12,14-ieoaaca-1,3,8,10-oao?aaeaeaoao?aa iaoieiaaeueoa a ea/anoaa eaoaeecaoi?a aeey ?aaoee?iaaiey iieaeoey?iie iannu iieeiaoae?eeaoia / A.A.A?eaeiaa, E.I.Aaeueaianeee, I.N.Aieeieiiia, ss.Ae.Eaiiaea, E.A.ssoeeie?neee // Aao. naeaeao. NNN? ?1306085 ii cayaea ?3906213 io 31.05.85 a., ca?aa. 12.12.86 a., N 08 F 2/38, 120/10. Eaiiaea ss.Ae. ?aaeien-?aaeoe?? oao?aaiiaeueieo eiiieaen?a i?eaeth(III,II), iiae?(III,II) oa eiaaeueoo(III,II) c iie?aeaioaoieie acioai?nieie e?aaiaeaie.- ?oeiien. Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy aeieoi?a o?i?/ieo iaoe ca niaoe?aeuei?noth 02.00.01 - iai?aai?/ia o?i?y.- ?inoeooo o?ce/ii? o?i?? ?i.E.A.Iena?aeaanueeiai IAI Oe?a?ie, Ee?a, 1998. Aeena?oaoe?y i?enay/aia aea/aiith oa?iiaeeiai?/iiai oa e?iaoe/iiai aniaeo?a ?aaeien-iiaaae?iee oao?aaiiaeueieo eiiieaen?a i?eaeth, i?ae? oa eiaaeueoo c iie?aeaioaoieie iae?ioeeee?/ieie oa a?aee?eoieaioethaiaeie acioai?nieie e?aaiaeaie. A ?iaio? cai?iiiiiaai? oeyoe oe?eani?yiiaaiiai oi?aae?iiy aaee/eiaie ?aaeien-iioaioe?ae?a ia? I???/??L (I=Ni, Cu) oeyoii aa??thaaiiy i?e?iaee aeiii?ieo aoii?a oa cai?niee?a a e?aaiaeao aai neeaaeo na?aaeiaeua. Anoaiiaeai? caaaeuei? e?iaoe/i? caeiiii??iino? ia?aa?ao oa?i?/ieo oa oioio?i?/ieo i?ioean?a aioo??oiueinoa?iiai a?aeiiaeaiiy iaoae?a(???) aei iaoae?a(??) ca ?aooiie ieeniaiiy aeaaoi??aeueiiai e?aaiaeo a eiiieaenao i?eaeth(???) ? i?ae?(???) aai aiiie?oe/iiai ?ic?eao ca’yceo eiaaeueo(???)-aaeiaai?ae /e eiaaeueo(???)-aee?e. Ciaeaeaiee iaa?aeiiee ?ai?oa i?ioean aaoieaoae?oe/iiai aiiie?co ca’yceo eiaaeueo-aoaeaoeue. Anoaiiaeai? iaoai?cie ?aaeoe?e ia?aiino aeaeo?iia c eiiieaen?a i?eaeth(??) ? i?ae?(??) ia ieenieee ??cii? i?e?iaee oa aeyaeai? eieeaaeuei? o?i?/i? ?aaeoe?? ca o/anoth iae?ioeeee?/ieo eiiieaen?a i?eaeth(???,??) ? a?iiaoo. ?ic?iaeai? i?ea?iaeuei? iaoiaee oaiieaoiiai neioaco iiaeo ooieoe?iiae?ciaaieo iiii- oa a?n(iae?ioeeee?/ieo) niieoe. Eeth/ia? neiaa: i?eaeue(???,??), i?aeue(???,??), eiaaeueo(???,??), oao?aaiiaeuei? eiiieaene, acaiae?ioeeee?/i? e?aaiaee, oaiieaoiee neioac, ?aaeien-iioaioe?aee, ia?aiin aeaeo?iia, e?iaoe/i? oa?aeoa?enoeee, eieeaaeuei? o?i?/i? ?aaeoe??. Eaiiaea ss.Ae. ?aaeien-?aaeoeee oao?aaiiaeueiuo eiiieaenia ieeaey(III,II), iaaee(III,II) e eiaaeueoa(III,II) n iieeaeaioaoiuie acioniaea?aeaueie eeaaiaeaie.- ?oeiienue. Aeenna?oaoeey ia nieneaiea o/aiie noaiaie aeieoi?a oeie/aneeo iaoe ii niaoeeaeueiinoe 02.00.01 - iai?aaie/aneay oeiey.- Einoeooo oece/aneie oeiee ei.E.A. Iena?aeaaneiai IAI Oe?aeiu, Eeaa, 1998. Aeenna?oaoeey iinayuaia enneaaeiaaieth oa?iiaeeiaie/aneiai e eeiaoe/aneiai aniaeoia ?aaeien-iiaaaeaiey oao?aaiiaeueiuo eiiieaenia ieeaey, iaaee e eiaaeueoa n iieeaeaioaoiuie iae?ioeeeee/aneeie e ioe?uoioeaiiuie acioniaea?aeaueie eeaaiaeaie. A ?aaioa i?aaeeiaeaiu iooe oeaeaiai?aaeaiiiai oi?aaeaiey aaee/eiaie ?aaeien-iioaioeeaeia ia? I???/??L (I=Ni, Cu) iooai aa?uee?iaaiey i?e?iaeu aeiii?iuo aoiiia e caianoeoaeae a eeaaiaeao eee ninoaaa n?aaeu. Onoaiiaeaiu iauea eeiaoe/aneea caeiiiia?iinoe i?ioaeaiey oa?ie/aneeo e oioioeie/aneeo i?ioeannia aioo?enoa?iiai ainnoaiiaeaiey iaoaeeia(???) aei iaoaeeia(??) ca n/ao ieeneaiey yeaaoi?eaeueiai eeaaiaea a eiiieaenao ieeaey(???) e iaaee(???) eee aiiieeoe/aneiai ?ac?uaa aeneaeueiie nayce eiaaeueo(???)-aaeiaaieae eeai eiaaeueo(???)-aeeee. Iaia?oaeai iaecaanoiue ?aiaa i?ioeann aaoieaoaeeoe/aneiai aiiieeca nayce eiaaeueo-oaea?iae. Onoaiiaeaiu iaoaieciu ?aaeoeee ia?aiina yeaeo?iia n eiiieaenia ieeaey(??) e iaaee(??) ia ieeneeoaee ?acee/iie i?e?iaeu e iaeaeaiu eieaaaoaeueiua oeie/aneea ?aaeoeee n o/anoeai iae?ioeeeee/aneeo eiiieaenia ieeaey(???,??) e a?iiaoa. ?ac?aaioaiu i?eaeiaeueiua iaoiaeu oaiieaoiiai neioaca iiauo ooieoeeiiaeece?iaaiiuo iiii- e aen(iae?ioeeeee/aneeo) niaaeeiaie. Eeth/aaua neiaa: ieeaeue(???,??), iaaeue(???,??), eiaaeueo(???,??), oao?aaiiaeueiua eiiieaenu, acaiae?ioeeeee/aneea eeaaiaeu, oaiieaoiue neioac, ?aaeien-iioaioeeaeu, ia?aiin yeaeo?iia, eeiaoe/aneea oa?aeoa?enoeee, eieaaaoaeueiua oeie/aneea ?aaeoeee. Lampeka Ya.D. Redox reactions of tetragonal nickel(III,II), copper(III,II) and cobalt(III,II) complexes with polydentate nitrogen-containing ligands.- Manuscript. Thesis for a doctor’s degree by speciality 02.00.01 - inorganic chemistry.- L.V.Pisar-zhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Kyiv, 1998. The investigation of thermodynamic and kinetic aspects of the redox behaviour of tetragonal nickel, copper and cobalt complexes with macrocyclic and open-chain nitrogen-containing ligands is the main aim of the dissertation. The approaches for the tuning of the I???/??L (I=Ni, Cu) couples redox potentials were developed based on the variations of the nature of donor atoms and substituents in the ligands as well as of the composition of medium. General kinetic trends of the proceeding of inner-sphere thermal and photochemical reactions of the reduction of metal(III) to metal(II) by equatorial ligands in the nickel(III) and copper(III) complexes as well as homolytic cleavage of axial cobalt(III)-halogenide or cobalt(III)-alkyl bonds were established. New unknown process of autocatalytic homolysis of cobalt-carbon bond was found. The mechanisms of the electron transfer from the nickel(II) and copper(II) complexes to oxidants of different nature were estimated and oscillating chemical reactions involving macrocyclic nickel(III,II) complexes and bromate were developed. Original approaches to the synthesis of new functionalized mono- and bis(macrocyclic) compounds were proposed. Key words: nickel(III,II), copper(III,II), cobalt(III,II), tetragonal complexes, azamacrocyclic ligands, template synthesis, redox potentials, electron transfer, kinetic characteristics, oscillating chemical reactions. PAGE PAGE 17 PAGE -(S(, Aeae/iieue E 32 41 45 39 35 33 40 31 39 43 30 37 31 40 44 38 30 32 33 41 38 37 (I(, eAeae/iieue 160 150 140 130 120 110 100 90 80 70 60 55 50 45 40 35 30 25 20 15 -(S(, Aeae/iieue E (-23 69 22 1 (-21 20 25 (-24 19 26 67 (-27 (-23 (-23 (-21 (-21 68 (-24 (-27 (-21 (I(, eAeae/iieue 160 140 120 100 80 60 40 75 70 65 60 55 50 45 40 35 30 ln(k12/f1/2) - W12 1 25 19 26 (-24 (-27 (-21 (-23 68 69 (-21 (-23 20 (-21 22 (-27 lnK12 -3 -4 -5 -6 -7 -8 -9 -10 24 22 20 18 16 14 12 10 8 6 i?iaeoeoe ?aeiia?iaoe?? aai aeeni?iii?oe?thaaiiy 4 k + S L (aai R) II Co + R . L II Co 3 k . L, R} II {Co 2 k 3 - k L III RCo L, R} II {Co . . (5) (4) (3) (2) . R . (1) i?iaeoeoe aca?iiae?? c ianoeith ?aaeeeae?a L, R} II {Co * n h {RCoL} L III RCo K 2 K 1 i?iaeoeoe ?aaeien-?iceeaaeo k 1 k 0 k 2 3+ L) 2 (H III M + + H 2+ (HL) III M + + H + L III M (S(, Aeae/iieue E 43 30 31 35 39 31 32 41 33 39 39 40 40 37 45 38 (H(, eAeae/iieue 100 50 0 -50 -100 -150 110 100 90 80 70 60 50 40 lgkniin (n-1) 37 33 32 30 41 35 39 41 33 30 32 31 31 40 37 38 39 43 Ef, B 1.0 0.0 -1.0 -2.0 -3.0 -4.0 -5.0 0.75 0.70 0.65 0.60 0.55 0.50 0.45 f, B 3 1 2 1.1 1.0 0.9 0.7 0.6 6 5 4 3 2 1 pH Ef, B pH 0.9 0.8 0.7 0.6 0.5 5 4 3 2 1 0 Af, A Af=-0,118[10Dq]+2,18 10 9 8 7 6 5 4 1 2 10Dq, 103 ni-1 a,b) ( 2 ) 3 R=(CH 3 R=CH R=H a,b) ( ?aoe a,b,g) ( iaci ?aoe iaci L29 L28 L27 L26 L25 L24 L23 L22 ) a,b,g,e ( L21 L20 L19 N N N N N N H N H N R R N H N N H N N N H H N H N N H N H H N H N N H N H H N H N N H N H H N H N

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