1

EUeA?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO ?iai? ?AAIA O?AIEA

NAIAIEOEI AeA??ss ?AAI?AIA

OAeE 541.49:546.267

Oe?AI?AeI? EIIIEAENE IA?AO?AeIEO IAOAE?A

C NIIEOEAIE, UI I?NOssOUe ACIO ? EENAIUe

02.00.01 – iai?aai?/ia o?i?y

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai noaiaiy

aeieoi?a o?i?/ieo iaoe

Euea?a – 1999

Aeena?oaoe??th ? ?oeiien

?iaioa aeeiiaia ia eaoaae?? aiae?oe/ii? o?i?? Aea?aeaaiiai oi?aa?neoaoo

“Euea?anueea iie?oaoi?ea” I?i?noa?noaa ina?oe Oe?a?ie

Io?oe?ei? iiiiaioe: aeieoi? o?i?/ieo iaoe, i?ioani?

Iaco?aiei ?aaai
Aiae??eiae/,

?inoeooo caaaeueii? oa
iai?aai?/ii? o?i??

?iai? A.?.Aa?iaaenueeiai
IAI Oe?a?ie,

caa?aeoaa/ a?aeae?eii

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

Eae?aaa/oe Aaeaioeia
Ieaenaiae??aia,

Iaoe?iiaeueiee iaaee/iee
oi?aa?neoao

?iai? I.I.Aiaiiieueoey,

caa?aeoaa/ eaoaae?e
caaaeueii? o?i??

aeieoi? o?i?/ieo iaoe,
aeioeaio

Iaaethe Aieiaeeie?
Aaneeueiae/,

Euea?anueeee aea?aeaaiee
oi?aa?neoao

?iai? ?aaia O?aiea,

i?ioani? eaoaae?e
iai?aai?/ii? o?i??

I?ia?aeia onoaiiaa: Ee?anueeee oi?aa?neoao ?iai? Oa?ana Oaa/aiea,
eaoaae?a

iai?aai?/ii? o?i??,
I?i?noa?noai ina?oe Oe?a?ie, i.Ee?a

Caoeno a?aeaoaeaoueny: “31” o?aaiy 1999 ?. i 14 aiaeei? ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee Ae 35.051.10 o Euea?anueeiio
aea?aeaaiiio oi?aa?neoao?

?iai? ?aaia O?aiea (290005, i. Euea?a, aoe. Ee?eea ? Iaoiae?y, 6)

C aeena?oaoe??th iiaeia iciaeiieoenue o a?ae?ioaoe? Euea?anueeiai
aea?aeaaiiai

oi?aa?neoaoo ?iai? ?aaia O?aiea ( 290005, i. Euea?a, aoe. Ae?aaiiaiiaa,
5)

Aaoi?aoa?ao ?ic?neaiee “26” ea?oiy 1999 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee
ss?aiei C.I.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue ?iaioe. O?i?y eii?aeeiaoe?eieo niieoe ? iaeiei c
?icae?e?a iai?aai?/ii? o?i??, yeee oni?oii ?icaeaa?oueny. Ca inoaii?
aeanyoee?ooy a oe?e aaeoc? iaa?iiaaeaeaii aaeeeee aenia?eiaioaeueiee
iaoa??ae, yeee aeicaieea c?iaeoe ia o?eueee oai?aoe/i? iaa?oiooaaiiy, a
e ciaeoe i?aeoe/ia canoinoaaiiy aaaaoueii eiiieaeniei niieoeai.

Na?aae eii?aeeiaoe?eieo niieoe aaeeeo ? aaaeeeao a?oio neeaaeathoue
eiiieaeni? oe?ai?aee ia?ao?aeieo iaoae?a, ye? oa?aeoa?ecothoueny
aaeeeith ??ciiiai?oi?noth aoaeiae, aeanoeainoae, aenieith i?oei?noth
ca’yceo Iaoaeo-eiiieaeniooai?thaa/a c oe?ai?aeieie e?aaiaeaie. E??i
oiai, oe?ai?ae-?iie caeaoi? noaa?e?coaaoe a aeaiaioao iaoa?aeoa?i?
nooiai? ieeniaiiy (Mo(0), W(0), V(0), Ti(0), W(V), Re(V), Mn(I) oa ?io?)
oa ooai?thaaoe eiiieaeni? oe?ai?aee c ??cieie eii?aeeiaoe?eieie /eneaie.

Oey a?oia eiiieaenieo niieoe ciaoiaeeoue ? oe?iea i?aeoe/ia
aeei?enoaiiy: ?aaaaioe a aiae?oe/i?e o?i??, i?ia?aeuei? oa?ae,
eaoae?caoi?e ?yaeo o?i?/ieo i?ioean?a, ?ia?a?oi?e ei?ic??, aoaeoeai?
?ii?oe, ni?aaioe, i?e ?icae?eaii? aeecueeeo ca aeanoeainoyie iaoae?a, ye
?ic/eie aeey aeaeo?io?i?/iiai aeae?eaiiy eieuei?iaeo ? ??aee?nieo
iaoae?a.

Oe?ai?aei? niieoee aeei?enoiaothoueny aeey neioaco, aeyaeaiiy ?
?icae?eaiiy i?aai?/ieo ?a/iaei, ye eaoae?caoi?e a ?yae? i?aai?/ieo
?aaeoe?e, ?i?oe?aoi?e i?ioean?a iie?ia?ec?oe??, ye? a?aeaoaathoueny o
aiaeieo ? iaaiaeieo na?aaeiaeuao. Aeyaeaiiy caeaoiino?
i?o?iciiaioaoe?aiioa?aoo iao??th cieaeoaaoe e?ia’yiee oene i?eaaei aei
i?aeaeuaiiy caoe?eaaeaiino? a aeine?aeaeaii? ci?oaiie?aaiaeieo
oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c i?aai?/ieie niieoeaie, ui
i?noyoue Acio, Eenaiue ? Noeueoo?.

A?eueoa /anoeia aeine?aeaeaiue, ui noinothoueny o?i?? eiiieaenieo
oe?ai?ae?a ia?ao?aeieo iaoae?a, i?enay/aia aea/aiith eiiieaen?a, ye?
i?noyoue iai?aai?/i? eao?iie o ciai?oi?e noa??. Aeey ieo ?ic?iaeaii
aeaoaeuei? iaoiaeeee neioaco, i?iaaaeaii aeine?aeaeaiiy ?o ??cieie
o?ceei-o?i?/ieie iaoiaeaie, c?iaeaii ocaaaeueiaiiy i?i aieea i?e?iaee
ciai?oiueinoa?ieo eao?ii?a, Iaoae?a-eiiieaeniooai?thaa/?a,
eii?aeeiaoe?eiiai /enea ia ?o no?oeoo?o oa aeanoeaino?.

A oie aea /an, oe?ai?aei? eiiieaene ia?ao?aeieo iaoae?a, ye? i?noyoue o
ciai?oi?e aai aioo??oi?e noa?ao Acio, Eenaiue, Oinoi?, Noeueoo?-ai?ni?
i?aai?/i? niieoee, aea/ai? cia/ii iaioa. A ?iaioao, i?enay/aieo
aeine?aeaeaiith oeeo eiiieaen?a, iienaii neioac, ?acoeueoaoe aeaiaioiiai
aiae?co ? i?aeoe/ii a?aenooi? aeai? c aeine?aeaeaiiy ?o aoaeiae,
i?e?iaee ca’yceo, iaoai?cio ooai?aiiy, oa?i?/ii? no?eeino? oa
iiaeeeainoae i?aeoe/iiai canoinoaaiiy.

Aeooaeueiei a ieai? i?aeoe/ii? ?aae?caoe?? ? aeine?aeaeaiiy oe?ai?aeieo
eiiieaen?a Oa?oio (II, III), ?ooai?th (II), Iie?aaeaio (IV), Eiaaeueoo
(III) c ai?aeii oa i?aai?/ieie niieoeaie, ui i?noyoue Acio ? Eenaiue, c
iaoith aea/aiiy ?o o?ceei-o?i?/ii? iiaaae?iee oa anoaiiaeaiiy
aca?iica’yceo neeaae-aoaeiaa-aeanoeaino?.

Ia iaio aeooaeueiei ? oaeiae aeine?aeaeaiiy ci?oaii-e?aaiaeieo
oe?ai?aeieo eiiieaen?a 3d-iaoae?a, ca’ycaia c aaaaeaiiyi a ?o neeaae
i?aai?/ieo e?aaiae?a, ui i?noyoue Eenaiue. Aeine?aeaeaiiy oaeeo
eiiieaen?a aeiaaa? a?aooaaiiy iniaeeainoae oe?ai?aeiiai e?aaiaeo,
iiaeeeaino? aca?iii? eii?aeeiaoe?? oe?ai?aeiiai oa i?aai?/iiai
e?aaiae?a, ?o aieeao ia oi?ioaaiiy eiiieaeno oa eiai aeanoeaino?.

Oae ye neioace oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c i?aai?/ieie
niieoeaie, ui i?noyoue Acio ? Eenaiue, o a?eueoino? aeiaaee?a
i?ioiaeyoue o na?aaeiaeu? i?aai?/ieo ?ic/eiiee?a, oiio ia?niaeoeaiei ?
aea/aiiy aieeao i?e?iaee iaaiaeiiai na?aaeiaeua ia ooai?aiiy oa
aeanoeaino? a?aeiia?aeieo eiiieaen?a.

*a?ac iaaeinoaoith aea/ai?noue aeanoeainoae oe?ai?aeieo eiiieaen?a c
i?aai?/ieie eao?iiaie aai e?aaiaeaie aaeueie ia?niaeoeaiei ? iiooe
iiaeeeaino? ?o i?aeoe/iiai aeei?enoaiiy.

O ca’yceo c neacaiei, aeine?aeaeaiiy oe?ai?aeieo eiiieaen?a c
niieoeaie, ui i?noyoue Acio ? Eenaiue, ? ia?niaeoeaiei a ieai?
anoaiiaeaiiy ei?aeyoe?eieo caeaaeiinoae i?ae neeaaeii, aoaeiaith oa
aeanoeainoyie.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, oaiaie, ieaiaie. Aeooaeuei?noue
?iaioe i?aeoaa?aeaeo?oueny aeeth/aiiyi ?? a Eii?aeeiaoe?eiee ieai
Iaoeiai? ?aaee AI N?N? c iai?aai?/ii? o?i?? ii oai? «Eii?aeeiaoe?ei?
niieoee. Neioac iiaeo oei?a eii?aeeiaoe?eieo niieoe ia iniia? oe?ai?ae?a
ia?ao?aeieo iaoae?a» (oeo? 2.17.2.1 1980-1985 ?.), a eii?aeeiaoe?eiee
ieai iaoeiai-aeine?aeieo ?ia?o «Caoeno iaoae?a a?ae ei?ic??» ii oai?
«?icaeoie oai?aoe/ieo iniia caoenii? ae?? ?ia?a?oi??a oa ?o
oe?eaiai?aaeaiiai neioaco» (oeo? 2.7.1.4. 1985-1990 ?., ?A-13245, ?
aea?aeaaii? ?a?no?aoe?? 01.85.000.5539 ?I.77.02 iino. I?aceae?? O?N?
?537 a?ae 1984 ?. oa ?57 a?ae 1987 ?.), eii?aeeiaoe?eiee ieai AI Oe?a?ie
» Neioac oa aeeaiea i/enoea iai?aai?/ieo niieoe» (1990-1995 ?.),
eii?aeeiaoe?eiee ieai IAI Oe?a?ie ii i?iaeai? «Iai?aai?/ia o?i?y»
(1995-1998 ?.).

?iaioa aeeiioaaeanue oaeiae o a?aeiia?aeiino? aei i?ia?aie Aea?aeaaiiai
Eii?oaoo Oe?a?ie c ieoaiue iaoee ? oaoiieia?e i?e Eaa?iao? I?i?no??a
Oe?a?ie ?5.2.1. «I?ioeei?ic?eiee caoeno iaoaeioiiaeo Oe?a?ie »
(1992-1995 ?.), caaaeaiiy 5.2.1.9 “?ic?iaea iaoeiaeo iniia noai?aiiy
?ia?a?oi??a ei?ic??, a?iei?ic?? oa ei?ic?eii-iaoai?/iiai ?oeioaaiiy
iaoae?a” (iino. ?12 AeEIO EIO a?ae 04.04. 1992 ?.), ? aea?aeaaii?
?a?no?aoe?? 01.93.UO 29969.

Aeeiiaiiy ?iaioe /anoeiai o?iainoaaeiny I?aeia?iaeiei oiiaeii
Aeae.Ni?ina (a?aio N APU053088).

Iaoa ? caaaeaiiy aeine?aeaeaiiy. Iaoa ?iaioe iieyaa? o aeyaeaii?
iniiaieo caeiiii??iinoae, ye? iathoue i?noea o i?ioean? aca?iiae?? Acio-
? Eenaiueai?nieo niieoe c i?inoeie ? eiiieaenieie oe?ai?aeaie
ia?ao?aeieo iaoae?a oa aeine?aeaeaii? o?ceei-o?i?/ieo aeanoeainoae
eiiieaen?a, ui ooai?eeeny.

Aeey aeinyaiaiiy aeaii? iaoe iaiao?aeii aoei ?ica’ycaoe oae? caaaeaiiy:

1. ?ic?iaeoe o?ceei-o?i?/i? iniiae neioaco oa neioacoaaoe oe?ai?aei?
eiiieaene ia?ao?aeieo iaoae?a c i?aai?/ieie niieoeaie, ui i?noyoue Acio
? Eenaiue o ciai?oi?e aai aioo??oi?e noa?ao, oa anoaiiaeoe neeaae
eiiieaen?a ? niin?a eii?aeeiaoe?? e?aaiae?a.

2. Ioe?ieoe aieea i?e?iaee N-, O-ai?nieo i?aai?/ieo eao?ii?a,
e?aaiae?a, iaoae?a-eiiieaeniooai?thaa/?a ia aoaeiao oe?ai?aeieo
eiiieaen?a.

3. Aea/eoe iniaeeaino? oa?i?/iiai ?iceeaaeo oe?ai?aeieo eiiieaen?a c
N-, O- ai?nieie i?aai?/ieie eao?iiaie. Anoaiiaeoe iine?aeiai?noue
o?ceei-o?i?/ieo i?ioean?a, ye? noi?iaiaeaeothoue ?iceeaae oe?ai?aeieo
eiiieaen?a. Aecia/eoe ei?aeyoe?th i?ae i?e?iaeith eao?iia,
Iaoaeo-eiiieaeniooai?thaa/a ? oaiia?aoo?aie oa?i?/ii? aeano?oeoe??
eiiieaen?a. I?iaanoe aiae?c e?iaoe/ieo ia?aiao??a oa?iie?co.

4. Aea/eoe aieea ai?ioiiieo ?ic/eiiee?a ia neioac oa ?aaeoe?eio
caeaoi?noue oe?ai?aeieo eiiieaen?a.

5. Aeine?aeeoe ?ia?aoth/? aeanoeaino? eiiieaen?a c iaoith anoaiiaeaiiy
iiaeeeaino? ?o i?aeoe/iiai canoinoaaiiy.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a. Aia?oa:

1. ?ic?iaeaii o?ceei-o?i?/i? iniiae neioaco iiaeo oe?ai?aeieo eiiieaen?a
c i?aai?/ieie Eenaiueaeiii?ieie e?aaiaeaie oa Acio- ? Eenaiueai?nieie
i?aai?/ieie eao?iiaie. Anoaiiaeaii neeaae oeeo oe?ai?aeieo eiiieaen?a oa
iiaeaii noaie ?o ooai?aiiy. Aeyniaii aieea i?e?iaee oeaio?aeueiiai ?iio
oa e?aaiae?a ia i?ioeane eiiieaeniooai?aiiy.

2. Aea/aii oa?aeoa? aca?iiae?? N-, O-ai?nieo i?aai?/ieo niieoe c
oe?ai?aeieie eeneioaie Fe(II, III), Ru (II), Mo (IV), Co (III).
Iieacaii, ui oey aca?iiae?y ia i?eaiaeeoue aei ?oeioaaiiy eiiieaeniiai
ai?iio, a i?e?aeiaiiy N-, O-ai?nieo niieoe a?aeaoaa?oueny c ooai?aiiyi
eiiieaenieo eao?ii?a.

3. Anoaiiaeaii aieea i?e?iaee, aoaeiae, iniiaiino? ciai?oiueinoa?ieo N-,
O-ai?nieo i?aai?/ieo eao?ii?a oa i?e?iaee Iaoae?a-eiiieaeniooai?thaa/?a
ia o?ceei-o?i?/i? aeanoeaino? oe?ai?aeieo eiiieaen?a.

4. Iieacaii, ui eiiieaene M(CN)2L, aea I=Mn2+, Co2+, Ni2+, L=DMSO, DMFA,
DMAA oa Co(CN)2xR3PO, aea R=NI3, x=1; C2H5, C4H9, C6H5, x=0,5
caa??aathoue iie?ia?io aoaeiao ? eii?aeeiaoe?y i?aai?/ieo e?aaiae?a
a?aeaoaa?oueny caaaeyee ooai?aiith aoiiaie iaoaeo ??cieo
eii?aeeiaoe?eieo aoce?a (MC4, MN4I2).

5. I?iaaaeaii aecia/aiiy e?enoae?/ii? no?oeoo?e eiiieaen?a
(DH)2[Fe(CN)5NO], (NH4)4[Mo(CN)8]0,5H2O oa (NH4)4[Ru(CN)6]. Aeyaeaii
iniaeeaino? i?inoi?iaiai ?ici?uaiiy eao?ii-ai?iia a ii??aeo nieyo
oe?aiieiiieaen?a. Anoaiiaeaii iniaeeaino? ca’yceo i?aai?/iiai
Eenaiueai?niiai eao?iio — ae?aioei??eeiaoai?th c eiiieaeniei oe?ai?aeiei
ai?iiii. Aia?oa anoaiiaeaii, ui a no?oeoo?? (NH4)4[Mo(CN)8]0,5H2O
eii?aeeiaoe?ei?e noa?? aoii?a Iie?aaeaio a?aeiia?aeathoue aeaa
iiiaia?aiieee — aeiaeaeaaae? ? aioei?ecia.

6. Noi?ioeueiaaii iniiai? caeiiii??iino? oa?i?/iiai ?iceeaaeo
oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c N-, O-ai?nieie i?aai?/ieie
eao?iiaie, ui neeaee iniiao iiaeaeueoiai ?icaeoeo oai?aoe/ieo oyaeaiue
i?i iaoai?ci oa?iie?co oe?ai?aeieo eiiieaen?a. Anoaiiaeaii ei?aeyoe?th
i?ae i?e?iaeith ciai?oiueinoa?ieo i?aai?/ieo eao?ii?a,
Iaoae?a-eiiieaeniooai?thaa/?a oa oa?i?/iith ? e?iaoe/iith no?ee?noth
eiiieaen?a. Anoaiiaeaii, ui ?yaee oa?i?/ii? no?eeino? oe?ai?aeieo
eiiieaen?a c N- ai?nieie i?aai?/ieie eao?iiaie ia ni?aiaaeathoue c
?yaeaie ?o e?iaoe/ii? no?eeino?. Iieacaii, ui aaee/eie aia?a??
aeoeaaoe?? oa ia?aaeaeniiiaioe?eiiai iiiaeieea caeaaeaoue a?ae i?e?iaee
ciai?oiueinoa?ieo eao?ii?a, Iaoae?a-eiiieaeniooai?thaa/?a oa
aeeaaeathoueny a ?aiee eiiiainaoe?eiiai aoaeoo.

7. I?iaaaeaii aeine?aeaeaiiy ?ia?aoth/eo aeanoeainoae oe?ai?aeieo
eiiieaen?a c N-, O-ai?nieie i?aai?/ieie niieoeaie a iaeo?aeueiiio
na?aaeiaeu? a i?enooiino? 3%-iiai ?ic/eio oei?eaeo iao??th, a ii?nuee?e
aiae?, a i?enooiino? noeueoao?aaeoeoth/eo aaeoa??e oa a eaeioa?aiaeo
iaoa??aeao.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a. I?aeoe/ia oe?ii?noue
?iaioe iieyaa? a oiio, ui a i?e:

1. ?ic?iaeaii iaoiaeeee neioaco oe?ai?aeieo eiiieaen?a ia?ao?aeieo
iaoae?a c N-, O-ai?nieie i?aai?/ieie eao?iiaie oa e?aaiaeaie.

2. Anoaiiaeai? caeiiii??iino? i?ae oiiaaie ?o iaea?aeaiiy, neeaaeii ?
o?ceei-o?i?/ieie aeanoeainoyie ? aeia?aeeiaei iaoa??aeii ? iiaeooue aooe
aeei?enoai? aeey ?aae?caoe?? ea?iaaiiai neioaco iiaeo oe?ai?aeieo
eiiieaen?a.

3. Aecia/aiiy e?enoae?/ii? no?oeoo?e eiiieaen?a aeaei iiaeeea?noue
iiynieoe iniaeeaino? ca’yceo i?ae N-, O-ai?niei eao?iiii ? oe?ai?aeiei
ai?iiii.

4. Anoaiiaeaii ? i?aeoaa?aeaeaii iaea?aeaiiyi i’yoe aaoi?nueeeo
na?aeioeoa iiaeeea?noue aeei?enoaiiy oe?ai?aeieo eiiieaen?a c N-,
O-ai?nieie i?aai?/ieie eao?iiaie aeey aioeei?ic?eiiai caoenoo noae? a
nenoaiao iai?ioiiai aiaeiiinoa/aiiy, a ii?nuee?e aiae?, a i?enooiino?
noeueoao?aaeoeoth/eo aaeoa??e. Iieacaia iiaeeea?noue aaaaeaiiy
oe?ai?aeieo eiiieaen?a a eaeioa?aia? iaoa??aee ? aeei?enoaiiy ?o aeey
caoenoo noaeueii? iiaa?oi? a?ae ei?ic?? oa a?iia?inoaiiy.

Iaea?aeai? ?acoeueoaoe iiaeooue aooe aeei?enoai? niaoe?ae?noaie i?e
aeine?aeaeaii? oe?ai?aeieo eiiieaen?a c iiaeie i?aai?/ieie Acio- ?
Eenaiueai?nieie niieoeaie, a oaeiae i?e /eoaii? niaoeeo?n?a, ui
aacothoueny ia aea/aii? eiiieaenieo niieoe.

Iniaenoee aianie caeiaoaa/a. Aeena?oaoe?eia ?iaioa a?oioo?oueny ia
iaoa??aeao iaoeiai-aeine?aeieo ?ia?o, aeeiiaieo aaoi?ii ca aeaniith
?i?oe?aoeaith, ye? aa?eoee a ieaie iaoeiai-aeine?aeii? ?iaioe aeeeaaea/a
aea?aeaaiiai oi?aa?neoaoo “Euea?anueea iie?oaoi?ea” ca 1975-1998 ??.
Aaoi?o iaeaaeeoue oai?aoe/ia iaa?oiooaaiiy caaaeaiiy, aeeiiaiiy,
ia?iaea, aiae?c, ?ioa?i?aoaoe?y ?acoeueoao?a aenia?eiaioaeueieo
aeine?aeaeaiue oa oi?ioethaaiy aeniiae?a. O aeeiiaii? aenia?eiaioaeueii?
/anoeie ?iaioe a?aee o/anoue ani??aioe Ai?iaa I.ss., Oacaae C.A.,
ni?aea??aieeii aeena?oaoe?eieo ?ia?o yeeo aoa aaoi? oa Eoioee I.?., c
yeei aaoi? ia? ni?euei? ioae?eaoe??.

Aeai? ?aioaaiino?oeoo?iiai aiae?co, ye? aeei?enoai? a ?iaio?, io?eiai?
a eaai?aoi??? iaoeiai-aeine?aeiiai O?ceei-o?i?/iiai ?inoeoooo ?i. E.ss.
Ea?iiaa ?AI ni?eueii c i?io. Aaeuenueeei A.E. oa ia eaoaae??
iai?aai?/ii? o?i?? Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo ?i. ?.O?aiea
ni?eueii c i?io. Ienuee?aei I.A. Iiiie?enoaee ieoaoe?aiiiie?aaeaoo (IV)
aiii?th neioaciaaii Coa?eoeueeithAe.?., a aaenaoe?aii?ooaiaoo (??)
aiii?th — Iei?nueeith A.I.

Aeine?aeaeaiiy ?ia?aoth/eo aeanoeainoae i?iaiaeeeiny /anoeiai o
O?ceei-iaoai?/iiio ?inoeooo? ?i. A.A. Ea?iaiea IAI Oe?a?ie ni?eueii c
e.o.i. Nii?oithe. I.A. oa e.o.i. Neiaiaeyi C.A.

*anoeia ?ia?o aeeiiaia ca ainiiaea?nueeeie ? aea?aeaaieie caiiaeaiiyie,
aea aeena?oaio aoea ea??aieeii aai a?aeiia?aeaeueiei aeeiiaaoeai. ?e
iaeaaeaoue ?ic?iaea i?ia?ai ? ieai?a oeeo ?ia?o oa ?o aaciina?aaei?
aeeiiaiiy.

Aianie aaoi?a o ?iaioe, ui aeeiiai? o ni?aaaoi?noa? ? aieiaiei ?
iieyaa? a iinoaiiaoe? caaaeaiiy aeine?aeaeaiiy, eiai iaoiaee/iiio oa
aenia?eiaioaeueiiio ae??oaii?, a ia?iaoe?, aiae?c? oa ?ioa?i?aoaoe??
iaea?aeaieo ?acoeueoao?a, oi?ioethaaii? oa iaa?oiooaaii? aeniiae?a.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iniiai? ?acoeueoaoe
aeena?oaoe?eii? ?iaioe aeiiia?aeaeeny ia O?O I?aeia?iaei?e eiioa?aioe??
c eii?aeeiaoe?eii? o?i?? (I?aaa, 1978), Oe?a?inueeeo ?anioae?eainueeeo
eiioa?aioe?yo c iai?aai?/ii? o?i?? (Aei?i?iiao?ianuee, 1977, 1981,
Oaeai?iae, 1986, 1992, N?ioa?iiieue, 1989), O?V Ananithci?e *oaa?anuee?e
ia?aae? c o?i?? eiiieaenieo niieoe (?aaiiai, 1981), OO?? I?aeia?iaei?e
eiioa?aioe?? c eii?aeeiaoe?eii? o?i?? (Aoaeaiaoo, 1982), ?V Ananithci?e
ia?aae? c eii?aeeiaoe?eieo niieoe Ni, Co, Mn (Oa?e?n?, 1983),
Ananithcieo eiioa?aioe?yo c oa?i?/iiai aiae?co (Oaeai?iae, 1985,
Eai?ia?aae, 1989), ? Oe?a?inuee?e ?anioae?eainuee?e eiioa?aioe?? c
oa?i?/iiai aiae?co eiiieaenieo niieoe (Oaeai?iae,1987), V? Ananithci?e
ia?aae? c o?i?? oa oaoiieia?? iie?aaeaio oa aieueo?aio (Iaeue/ee, 1988),
Naeoe?? iaoeiai? ?aaee AI O?N? c i?iaeaie «Iai?aai?/ia o?i?y» (Euea?a,
1983) ? c i?iaeaie «Neioac oa aeeaiea i/enoea iai?aai?/ieo niieoe»
(Euea?a, 1988), Ananithci?e oeie?-nai?ia?? c ei?ic?? (N?ioa?iiieue,
1991), ? neiiic?oi? o?i?/ii? eii?n?? IOO (Euea?a, 1993), I?aeia?iaeiiio
nai?ia?? «A?I-94», “A?I-97” (Aeiiaoeuee, 1994, 1997), I?aeia?iaeiiio
nai?ia??-aenoaaoe? c ei?ic?? (Euea?a,1994), XIV Oe?a?inuee?e
eiioa?aioe?? c iai?aai?/ii? o?i?? (Ee?a, 1996), ae?caei?e nan?? Iaoeiai?
?aaee c i?iaeaie “Iai?aai?/ia o?i?y” IAI Oe?a?ie (Oaeai?iae, 1998).

Ioae?eaoe??. Aeena?oaoe?y iaienaia ia iniia? iaoa??ae?a 44 noaoae, ye?
iioae?eiaai? o a?o/eciyieo (Oe?a?inueeee o?i?/iee aeo?iae, A?niee
aea?aeaaiiai oi?aa?neoaoo «Euea?anueea iie?oaoi?ea», O?ceei-o?i?/ia
iaoai?ea iaoa??ae?a), ?aaeyinueeeo, a i?ci?oa ?in?enueeeo (AEo?iae
iai?aaie/aneie oeiee, aeo?iae «Eii?aeeiaoeeiiiay oeiey»,
E?enoaeeia?aoey) aeo?iaeao, 26 oac aeiiia?aeae ia iaoeiaeo eiioa?aioe?yo
??ciiai ??aiy oa 5 aaoi?nueeeo na?aeioeoa.

No?oeoo?a oa ia’?i aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny ?c anooio,
7 ?icae?e?a, aeniiae?a, nieneo aeei?enoaii? e?oa?aoo?e ?c 363
iaeiaioaaiue ?ia?o a?o/eciyieo oa ca?oa?aeieo aaoi??a.

?iaioa aeeeaaeaia ia 303 noi??ieao iaoeiiieniiai oaenoo, i?noeoue 56
?enoie?a, 56 oaaeeoeue, aeiaeaoie ia 36 noi??ieao.

INIIAIEE CI?NO ?IAIOE

Iniiai? ?acoeueoaoe ?iaioe iaea?aeai? i?e aeine?aeaeaii? oe?ai?aeieo
eiiieaen?a ia?ao?aeieo iaoae?a c niieoeaie, ui i?noyoue Acio ? Eenaiue.

Na?aae aaeeei? e?eueeino? ia?ao?aeieo iaoae?a aeey aeine?aeaeaiiy
oe?ai?aeieo eiiieaen?a aea?aii Iaiaai, Oa?oi, Eiaaeueo, I?eie, ye?
iaeaaeaoue aei iaeiiai ia??iaeo, iathoue aeecuee? eiii? ?aae?one, aaaaoi
ni?eueieo aeanoeainoae, aea iathoue ? ?yae nooo?aeo a?aei?iiinoae, a
oaeiae aeaiaioe-aiaeiae ?ooai?e ? Iaeaae?e, aeey yeeo iiaeia i/?eoaaoe
ooai?aiiy aiaeia?/ieo niieoe, oa Iie?aaeai, yeee cia/ii a?ae??ciy?oueny
ca nai?ie aeanoeainoyie a?ae aeacaieo iaoae?a.

Na?aae niieoe, ye? i?noyoue o nai?io neeaae? Acio aai Eenaiue, aea?aii:
ai?ae, ae?oaoe/i?, a?iiaoe/i? iiii- oa iie?aeaioaoi? ai?ie,
aaoa?ioeeee?/i? Acioai?ni? niieoee, i??acieiie, a?ae?aceaee ea?aiiiaeo
eeneio, ae?aioei??eeiaoai oa eiai iio?aei?, aeeiaoeenoeueoieneae,
aeeiaoeeoi?iai?ae, aeeiaoeeaoeaoai?ae, oino?iieneaee.

Aea?? oeeo niieoe coiiaeaiee oei, ui aeaye? ?o i?aaenoaaieee iieacaee
naith ia?niaeoeai?noue aeey i?aeoe/iiai aeei?enoaiiy. Oiio aeooaeueiei ?
iaea?aeaiiy oa iiaeaeueoa aea/aiiy oe?ai?aeieo eiiieaen?a c niieoeaie,
ui i?noyoue Acio ? Eenaiue, iniaeeai oeo, ye? iiaeooue i?iyaeyoe
neia?a?/io ae?th caaaeyee ii?aeiaiith a?ieia?/ii? aeoeaiino? eao?iiii?
oa ai?iiii? neeaaeiaeo eiiieaeno. E??i oiai, neioac aaaaoueio
oe?ai?aeieo eiiieaen?a i?ioiaeeoue a iaaiaeieo ?ic/eiao ? aaaeeeaith
i?iaeaiith ? ia?aaaaeaiiy ?o o ?ic/eiiee noai. Oe?ai?aei? eiiieaene
ia?aaaaeii ?niothoue a ai?iiiiio noai? ? ?o ?ic/eii?noue a i?aai?/ieo
?ic/eiieeao caeaaeeoue a?ae i?e?iaee i?ioe?iio. sseui i?ioe?iiii ? eiie
iaoae?a, oi oae? eiiieaene ia?ic/eii? a i?aai?/ieo ?ic/eiieeao. Oiio i?e
neioac? iiaeo oe?ai?aeieo eiiieaen?a a iaaiaeieo na?aaeiaeuao ii/aee
aeei?enoiaoaaoe i?aai?/i? eao?iie oeio “aiii?th”, “ienii?th”,
“oinoii?th”. Oe?ieee aea?? ??cieo eean?a N-, I-, ?-, S-ai?nieo
i?aai?/ieo niieoe aeicaiey? neioacoaaoe iia? oe?ai?aei? eiiieaene oa
ananoi?iiiuei aeine?aeeoe ?o ?ieue a o?i?? oe?ai?aeieo eiiieaen?a.

?icae?e 1 i?enay/aiee ?icaeyaeo aeaieo e?oa?aoo?e, ye? noinothoueny
oiia neioaco, ?acoeueoao?a o?ceei-o?i?/iiai aeine?aeaeaiiy, anoaiiaeaiiy
aoaeiae oa iiaeeeainoae aeei?enoaiiy oe?ai?aeieo eiiieaen?a ia?ao?aeieo
iaoae?a c N-, O-ai?nieie eao?iiaie aai e?aaiaeaie. C i?iaaaeaiiai
iaeyaeo c?iaeaii aeniiaie i?i iaaeinoaoith aea/ai?noue aieeao i?e?iaee
ciai?oiueinoa?ieo ii??aeo eao?ii?a oa I-ai?nieo i?aai?/ieo e?aaiae?a,
Iaoae?a-eiiieaeniooai?thaa/?a, i?e?iaee aiaeiiai ? iaaiaeiiai
na?aaeiaeua ia o?ceei-o?i?/i? aeanoeaino? (aoaeiao, ?aaeoe?eio
caeaoi?noue oa oa?i?/io no?ee?noue) oe?ai?aeieo eiiieaen?a oa
iaaeinoaoith iiaeeea?noue ?o i?aeoe/iiai canoinoaaiiy.

?icae?e 2 ?iaioe i?enay/aiee ?ic?iaoe? o?ceei-o?i?/ieo iniia neioaco
oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c niieoeaie, ui i?noyoue Acio
? Eenaiue.

Ceioac oe?ai?aeieo eiiieaen?a i?a?ao?aeieo iaoae?a c Acioai?nieie
ii??aeie eao?iiaie i?ioiaeeoue ca ?aaeoe??th, yeo iiaeia iienaoe
??aiyiiyi:

nA + H4[M(CN)m] = (AH)nH4-n[M(CN)m],

aea A — N-ai?nia i?aai?/ia niieoea, n = 1-4, M = Fe2+, Ru2+, m = 6; M =
Mo4+, m = 8.

Neioaciaai? eiiieaene neeaaeo: [AH]H3[Fe(CN)6], aea A-aeeoai?eai?i;
[AH]2H2[I(CN)m], aea A-o?eaoeeai?i, aoeeaiae?ai?i, i-oie?aeei,
1,2,3-aaicio?eacie, 1-oai?e-2,3-aeeiaoee-4-ai?iii??acieii-5
(4-ai?iiaioei??ei), a?ae?aceae ?cii?eioeiiai? eeneioe (ooaaceae);
[AH]3H[Fe(CN)6], aea A-aaiceaeei; [AH]4[I(CN)m], aea A-ae?aoeeai?i,
aooeeai?i, aoeeaiae?ai?i, aaiceeai?i, 2-ai?iii??eaeei, oai?ea?ae?acei,
i-oieo?aeei, i-ai?ceaeei, i-enee?aeei, 1-, 2-iaooeeai?ie, i-ai?iioaiie,
1-oai?e-2,3-aeeiaoee-4-aeeiaoeeai?ii-i??acieii-5 (ai?aeii??ei),
1-oai?e-2,3-aeeiaoee-4-iaoeeai?iii??acieii-5-N-iaoainoeueoiiao iao??th
(aiaeuea?i), 3-iaoiene-4-ieneaaicee?aeaia?ae?aceae ?cii?eioeiiai?
eeneioe (ooeaaceae), a?ae?aceaee ioeoiai?, iaooieii?, iaooeeioeoiai? oa
a?iiaaicieii? eeneio; [AH2]2[I(CN)6], aea M=Fe2+, Ru2+, A —
ae?aoeeaio?eai?i, aaenaiaoeeaiae?ai?i.

Neioac oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c Eenaiueai?nieie
ii??aeie eao?iiaie i?ioiaeeoue ca aiaeia?/iith ?aaeoe??th:

Hn[M(CN)m] + xD (DH)xHn-x[M(CN)m],

aea D — ae?aioei??eeiaoai, i?ii?e- ? aaeneeae?aioei??eeiaoai, n = 2-4, x
= 2, 4, m = 6, 8, M = Fe2+, Fe3+, Co3+, Mo4+.

Neioac oe?ai?aeieo aaeoeo?a ia?ao?aeieo iaoae?a oeio M(CN)2L, aea M =
Mn2+, Co2+, Ni2+; L-aeeiaoeenoeueoieneae, aeeiaoeeoi?iai?ae,
aeeiaoeeaoeaoai?ae, oino?i-ieneaee i?iaiaeeee a na?aaeiaeu? i?aai?/ieo
?ic/eiiee?a ca ?aaeoe??th

MNl2Ln+2NH4CN=M(CN)2L+(n-1)L+2NH4Cl.

Aia?oa ye oe?aioth/ee aaaio aeei?enoaii oe?ai?ae aiii?th, yeee, ia
a?aei?io a?ae oe?ai?ae?a eae?th aai iao??th, aeia?a ?ic/eiy?oueny a
iiey?ieo i?aai?/ieo ?ic/eiieeao.

O iaaiaeiiio na?aaeiaeu? neioacoaaee oaeiae eiiieaene:
(NH4)2[Co(CN)5L], aea L-aeeiaoeenoeueoieneae aai aeeiaoeeoi?iai?ae ca
?aaeoe??th:

4Co(CN)2L + 12 NH4CN + O2 = 4 (NH4)2[Co(CN)5L] + 4NH3 + 2H2O.

I?e ae?? iaaeeeoeo NH4CN ia a?ia?i? oe?ai?aee Co, Ni, Pd a na?aaeiaeu?
DMSO, DMFA ca ?aaeoe??th:

M(CN)2+(n-2)NH4CN(NH4)n-2[M(CN)n], aea M=Co, Ni, Pd,

iaea?aeaii eiiieaene (NH4)6[Co2(CN)10]3DMFA (aeeia?i?noue eiiieaeno
anoaiiaeaia ca ?acoeueoaoaie iaai?oieo aei??thaaiue), (NH4)2[Ni(CN)4],
(NH4)2[Pd(CN)4]3DMSO, neioac yeeo c aiaeieo ?ic/ei?a oo?oaeiaiee aai
iaiiaeeeaee.

Aeey neioaco Ag3[Mo(CN)7DMSO] aeei?enoiaoaaee aeeiaoeenoeueoieneaeiee
?ic/ei ieoaoe?aiiiie?aaeaiiai? (IV) eeneioe, ii?ii?iaiee OO na?oeii. I?e
oeueiio a ?ic/ei? a?aeaoaathoueny ?aaeoe??:

H4[Mo(CN)8] + DMSO wmetafile8? ??O????????????
???????????yyy????.????1?????? ???????
Aa???&??yyyy?????Ayyy?yyy ??s?? ???&?
?MathType??0????u?th??????H3[Mo(CN)7DMSO]+3AgClO4
=Ag3[Mo(CN)7DMSO]+3HClO4.

?ic?iaeaii o?ceei-o?i?/i? iniiae neioaco ? neioaciaaii 89 (aia?oa 80)
oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c niieoeaie, ui i?noyoue Acio
? Eenaiue o ciai?oi?e oa aioo??oi?e noa?ao. Neeaae eiiieaen?a
anoaiiaeaii ca ?acoeueoaoaie aeaiaioiiai aiae?co ia ai?no a?aeiia?aeiia
d-Iaoaeo, Aoaeaoeth, Aiaeith, Acioo oa aiaee. Cai?iiiiiaai? iaoiaeeee
iiaeooue aooe aeei?enoai? aeey neioaco ?ioeo aiaeia?/ieo eiiieaen?a.

A ?icae?e? 3 ?icaeyiooi iniaeeaino? aoaeiae oe?ai?aeieo eiiieaen?a
ia?ao?aeieo iaoae?a c niieoeaie, ui i?noyoue Acio ? Eenaiue. Aiae?c ?*
niaeo??a oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c N-, O-ai?nieie
i?aai?/ieie eao?iiaie iieacaa, ui a niaeo?ao on?o eiiieaen?a
niinoa??aa?oueny e?eueea oa?aeoa?enoe/ieo nioa iiaeeiaiiy i?e ??cieo
cia/aiiyo oaeeueiaiai /enea.

A ae?eyioe? 2000-2140 ni-1 niinoa??aa?oueny aocueea ?ioaineaia nioaa
iiaeeiaiiy aaeaioieo eieeaaiue oe?aiia?oie ((CN)) aeey iai?noeiaeo ? a
ae?eyioe? 2150-2180 ni-1 aeey i?noeiaeo oe?aiia?oi. ?ici?uaiiy (CN) a
o?e /e ?io?e ae?eyioe? oa ?? ?icuaieaiiy neoaeeoue e?eoa???i ??cii?
i?e?iaee oe?aiia?oi.

A iecueei/anoioi?e ae?eyioe? niinoa??aathoueny aaeaioi? eieeaaiiy
ca’yce?a Iaoae-Aoaeaoeue ((M-C)=520-600 ni-1) ? aeaoi?iaoe?ei? eieeaaiiy
eoo?a Iaoae-Aoaeaoeue-Acio ((M-CN)=410-500 ni-1).

Iieaeoee e?enoae?caoe?eii? aiaee aeathoue aea? nioae iiaeeiaiiy s(OH),
as(OH) i?e 3400-3600 ni-1 oa (HOH) i?e 1600-1640 ni-1.

A ?* niaeo?ao oe?ai?aeieo eiiieaen?a Oa?oio (??), ?ooai?th (??),
Iie?aaeaio (?V) c N-ai?nieie ii??aeie eao?iiaie o aeniei/anoioi?e
ae?eyioe? 2390-3250 ni-1 niinoa??aathoueny s ? as eieeaaiiy i?ioiiiaaieo
ai?iia?oi NHn+ (n=1, 2, 3) o aeaeyae? oe?iei? nioae. Nioae iiaeeiaiiy
aeaoi?iaoe?eieo eieeaaiue i?ioiiiaaieo ai?iia?oi niinoa??aathoueny a
ae?eyioe? as (NHn+) 1495-1625 ? s(NHn+) 1290-1390 ni-1, a nioae
aaeaioieo eieeaaiue (C-N) a ae?eyioe? 1047-1290 ni-1.

O aeiaaeeo aca?iiae?? oe?ai?aeieo eeneio Fe(II), Ru(II), Mo(IV) c
aoeeaiae?ai?iii, ae?aoeeaio?eai?iii, aaiceaeeiii, i-oie?aeeiii,
aaenaiaoeeaiae?ai?iii, ye? i?noyoue aea? aai o?e ai?iia?oie, iiaeooue
ooai?thaaoeny eiiieaene ??ciiai neeaaeo a caeaaeiino? a?ae oiai,
aoaeooue oe? niieoee iiii /e aea?/? i?ioiiiaaieie.

Ia ?en.1 cia?aaeaii ?* niaeo?e iiaeeiaiiy aoeeaiae?ai?iiaeo oe?ai?aeieo
eiiieaen?a Oa?oio, ?ooai?th oa Iie?aaeaio.

Iayai?noue oe?iei? nioae iiaeeiaiiy aaeaioieo eieeaaiue i?ioiiiaaieo
a?oi (NH3+) ? aeaoi?iaoe?eieo eieeaaiue s(NH3+), as(NH3+) a oeeo
eiiieaenao ii?yae c nioaaie iiaeeiaiiy iai?ioiiiaaieo ai?iia?oi ?
aeieacii i?ioii?caoe?? aoeeaiae?ai?io ii iaei?e ai?iia?oi? i?e
aca?iiae?? c iacaaieie eeneioaie. Oiio neeaae oeeo eiiieaen?a
a?aeiia?aea? oi?ioeai: [H2NCH2CH2NH3]4[Fe(CN)6],
[H2NCH2CH2NH3]4[Ru(CN)6] ? [H2NCH2CH2NH3]4[Mo(CN)8].

A niaeo?ao ae?aoeeaio?eai?iiaeo eiiieaen?a Oa?oio ? ?ooai?th o
aeniei/anoioi?e ae?eyioe? i?e 3380 ? 3425 ni-1 a?aeiia?aeii, aeyaeaii
oe?iea nioaa iiaeeiaiiy, yea iiaea aooe a?aeianaia aei aaeaioieo
eieeaaiue iai?ioiiiaaieo a?oi NH ? a?aenooi? nioae iiaeeiaiiy, ye?
a?aeiia?aeaee a eieeaaiiyi iai?ioiiiaaieo a?oi NH2. I?ioa a niaeo?ao
aaenaoe?aiioa?aoo (??) oa aaenaoe?aii?ooaiaoo (??) ae?aoeeaio?eaiii?th
niinoa??aathoueny (NH3+) i?e 2480-3200 ?

2500-3200; as(NH3+) i?e 1520-1625 ? 1535-1565; s(NH3+) i?e 1315 ? 1315
ni-1 a?aeiia?aeii, ui aeaco? ia oa, ui i?e aca?iiae?? ae?aoeeaio?eai?io
c oe?ai?aeieie eeneioaie a?aeaoaa?oueny i?ioii?caoe?y iaio ia?aeiieo
ai?iia?oi NH2, ye? iathoue a?eueo iniiai? aeanoeaino? (pKb1=3,95,
pKb2=4,6), a aoi?eiia ?i?iia?oia ia i?ioii?co?oueny (pKb3=9,1). Oiio
neeaae eiiieaen?a a?aeiia?aea? oi?ioe? [NH(CH2CH2NH3)2]2[M(CN)6], aea M
= Fe2+, Ru2+.

Aaiceaeei NH2(C6H4)2NH2 ? i-oie?aeei NH2(C6H3)2(CH3)2NH2 i?e aca?iiae??
c oe?ai?aeieie eeneioaie i?ioii?cothoueny o?eueee ii iaei?e ai?iia?oi?,
i?e/iio, a iaio aeiaaeeao ooai?ththoueny eene? nie? neeaaeo:
[NH2(C6H3)2(CH3)2NH3]2H2[M(CN)n]xH2O (aea M = Fe2+, Ru2+, n=6, x=1;
Mo4+, n=8, x=4) ? [NH2(C6H4)2NH3]3H Fe(CN)n], ui anoaiiaeaii ca
?acoeueoaoaie aiae?co.

Ia a?aei?io a?ae aeua neacaiiai i?e aca?iiae?? aaenaiaoeeaiae?ai?io,
yeee ? aeineoue neeueiith iniiaith (?E1 =2,9, ?E2=4,0) c
aaenaoe?aiioa?aoiith (??) eeneioith a?aeaoaa?oueny i?ioii?caoe?y aeaio
ai?iia?oi -NH2, ui i?aeoaa?aeaeo?oueny a?aenooi?noth a ?* niaeo?ao nioa
iiaeeiaiiy iai?ioiiiaaieo ai?iia?oi ? neeaae eiiieaeno a?aeiia?aea?
oi?ioe? [H3N(CH2)6NH3]2[Fe(CN)6]2H2O (?en. 2).

Aaeeea a?oia oe?ai?aeieo eiiieaen?a Oa?oio, ?ooai?th oa Iie?aaeaio
i?noeoue a ciai?oiueinoa?iiio eao?ii? a?iiaoe/i? niieoee. A ?* niaeo?ao
oeeo eiiieaenieo niieoe a ae?eyioe? 2540-3040, 1505-1595, 1310-1390 ni-1
niinoa??aathoueny aaeaioi? oa aeaoi?iaoe?ei? eieeaaiiy i?ioiiiaaieo
ai?iia?oi NH3+ (aeey 1,2,3-aaicio?eacieo NH2+). ?* niaeo?
aaenaoe?aiioa?aoo (II) aeeoai?eaiii?th aeaui a?ae??ciy?oueny a?ae
niaeo??a oa?ioe?ai?aeieo (II) eiiieaen?a c a?iiaoe/ieie ai?iaie.

Aeeoai?eai?i ? aeoaea neaaeith iniiaith, eiai NH-a?oia «cae?eoa» ?,
i/aaeaeii, /a?ac noa?e/i? o?oaeiiu? i?e aca?iiae?? c H4[Fe(CN)6]
ooai?th?oueny eenea n?eue [(C6H5)2NH2]H3[Fe(CN)6]. E??i oiai,
aeeoai?eai?i, iiae?aii aei 1,2,3-aaicio?eacieo, cnoaa? nioao aaeaioieo
eieeaaiue ca’yceo CN o aeniei/anoioio ae?eyieo.

A ?* niaeo?ao [C5H4NNH3]4[M(CN)6] (M = Fe2+, Ru2+, n=6; Mo4+, n=8)
niinoa??aathoueny nioae aaeaioieo eieeaaiue i?ioiiiaaieo ai?iia?oi a
ae?eyioe? 2680-3200, as(NH3+) i?e 1520-1624, s(NH3+) i?e 1290-1320 ni-1,
ui aeaco? ia oa, ui i?e ooai?aii? ii??aiai eao?iio a?aeaoaa?oueny
i?ioii?caoe?y a?oie NH2 2-ai?iii??eaeeio. Nioae iiaeeiaiiy, ye?
a?aeiia?aeathoue iiaeeiaiith aoii?a Acioo aaoa?ioeeeeo (742, 775, 960,
990, 1275, 1555) iaei ci?iththoueny.

Oa?aeoa? aca?iiae?? H4[Fe(CN)6], H4[Ru(CN)6] ? H4[Mo(CN)8] c
1-iaooeeai?iii /e 2-iaooeeai?iii ia ci?ith?oueny. A ?* niaeo?ao iaio
eiiieaen?a nioae iiaeeiaiiy (NH3+), as(NH3+) i s(NH3+) iaeaea iaiaeia?,
ui na?ae/eoue i?i iacia/iee aieea iaooieiiai e?eueoey ia oeth
aca?iiae?th.

Oaeei /eiii, iayai?noue a niaeo?ao eiiieaen?a nioa iiaeeiaiiy
i?ioiiiaaieo ai?iiaoi aeaco? ia oa, ui aca?iiae?y Acioai?nieo i?aai?/ieo
niieoe c oe?ai?aeieie eeneioaie Oa?oio, ?ooai?th, Iie?aaeaio ia
i?eaiaeeoue aei ?oeioaaiiy eiiieaenieo ai?ii?a, a ?o i?e?aeiaiiy
a?aeaoaa?oueny c ooai?aiiyi ii??aeo eao?ii?a.

Ie?aia i?noea na?aae aea/aieo niieoe caeiathoue oe?ai?aei? eiiieaene
Oa?oio (??) c iio?aeieie i??acieii?a oa a?ae?aceaeaie aeayeeo ea?aiiiaeo
eeneio, ye? i?noyoue ii aea? ?aaeoe?eii-caeaoi? a?oie NHn (n=1, 2) ?
CO.

Aca?iiae?y H4[Fe(CN)6] c oaie?a?ae?aceiii oa a?ae?aceaeaie aoeaoaoii?,
1-iaooieii?, 1-iaooeeaoeaoaoii?, a?iiaaicieii? eeneio a?aeaoaa?oueny ca
?aooiie i?ioii?caoe?? a?oie -NH2, i?i ui na?ae/eoue ci?uaiiy aaeaioieo
nioa iiaeeiaiiy ca’yce?a N-H o iecueei/anoioio ae?eyieo ia ~200 ni-1.
Aeey oeeo niieoe iieiaeaiiy nioae iiaeeiaiiy aaeaioieo eieeaaiue
ea?aii?eueii? a?oie iaeaea ia ci?ith?oueony o ii??aiyii? ?c cia/aiiyie
aeey aeo?aeieo a?ae?aceae?a.

A oie aea /an o ?* niaeo?ao aaenaoe?aiioa?aoo (??) ooaaceae?th ?
ooeaaceae?th oa a niaeo?ao iio?aeieo i??acieii?a — aaenaoe?aiioa?aoao
(??) 4-ai?iiaioei??ei?th, ai?aeii??ei?th oa aiaeuea?i?th aeiaeaoeiai
niinoa??aa?oueny ci?uaiiy nioa iiaeeiaiiy aaeaioieo eieeaaiue
ea?aii?eueii? a?oie (N=I) ia 20-35 ni-1. Oea aeaco? ia iiaeeeao o/anoue
a?oie N=I a ooai?aii? ii??ai? nie? /a?ac aeieeiaiiy ca’yce?a N-I…I,
iiae?aii ye a eiiieaenao oe?ai?aeieo eeneio Fe(II, ???), Co(III) c
ae?aioei??eeiaoaiii.

Oaeei /eiii, i?e aca?iiae?? oe?ai?aeieo eeneio ia?ao?aeieo iaoae?a c
i?aai?/ieie niieoeaie, ye? i?noyoue iaeii/anii ai?ii- ? ea?aii?euei?
a?oie, ooai?aiiy ii??aeo nieae iiaea a?aeaoaaoeny ca ?aooiie iaio a?oi.

O aeiaaeeo aca?iiae?? oe?ai?aeieo eeneio c ae?aioei??eeiaoaiii oa eiai
iio?aeieie (DH)oIn-x[M(CN)m] ( M=Fe2+, Fe3+, Co3+, Mo4+) ooai?aiiy
ii??aeo nieae a?aeaoaa?oueny ca ?aooiie i?ioii?caoe?? aoiio Eenith c
ooai?aiiyi eao?iio DH+. A ?* niaeo?ao oea i?iyaey?oueny cnoaii nioae
iiaeeiaiiy i?e 1660 ni-1 aaeaioieo eieeaaiue ca’yce?a C=O a?eueiiai
ae?aioei??eeiaoaio aei 1610 ni-1 o eiiieaenao.

Oaeei /eiii, niieoee (DH) oIn-x[M(CN)m] a?aeiinyoueny aei eiiieo
ii??aeo nieae oe?ai?aeieo eeneio, ye? ca nai?th no?oeoo?ith
a?ae??ciythoueny a?ae iai?aai?/ieo nieae a?aeiia?aeieo oe?ai?aeieo
eeneio.

Ia ?enoieo 3 cia?aaeaii caeaaei?noue /anoioe aaeaioieo eieeaaiue (CN)
oa?i-, ?ooaii- oa iie?aaeaiioe?ai?aeieo eii?a a?ae iniiaiino?
ae?oaoe/ieo ai?i?a, ye? aoiaeyoue a ii??aee eao?ii. I?e ciaioaii?
iniiaiino? ai?io cia/aiiy (CN) caeeoathoueny iaeaea aac ci?i, ca
ie?aieie aeiyoeaie. Ca?aene iiaeaii c?iaeoe aeniiaie, ui i?e?iaea
ae?oaoe/ieo ai?i?a iaei aieeaa? ia /anoioo (CN) oe?ai?aeieo ai?ii?a.
Oea, i/aaeaeii, ca’ycaia c oei, ui N-ai?ni? ii??a? eao?iie nooo?ai ia
ci?iththoue i?eioeeiiao aoaeiao oe?ai?aeieo ai?ii?a.

Ae?oao aaeeeo a?oio noaiiaeyoue eiiieaene, ye? a ii??aiio eao?ii?
i?noyoue neaae? iniiae ??cii? i?e?iaee (?en. 4). sse aeaeii c
iaea?aeaieo aeaieo, oa?aeoa? ci?ie /anoioe aaeaioieo eieeaaiue (CN) a?ae
aaee/eie pKb i?aai?/ieo ai?i?a, ye? aoiaeyoue a ii??aee eao?ii, aeey
oe?ai?aeieo eiiieaen?a Oa?oio (II), ?ooai?th (II), Iie?aaeaio (IV)
iiae?aiee i?ae niaith oa caeaaeeoue a?ae i?e?iaee i?aai?/ii? iniiae,
a?ae iieiaeaiiy ? i?e?iaee cai?niee?a a i?aai?/ieo ai?iao, a?ae ?ici??o
ciai?oiueinoa?iiai eao?iio, a?ae i?e?iaee oa nooiaiy ieeniaiiy
Iaoaeo-eiiieaeniooai?thaa/a. Oae, 2-ai?iii??eaeei ? 1,2,3-aaicio?eacie,
ye? iathoue aeiaeaoeia? i?ioiiiaeoeaioi?i? oeaio?e, cnoaathoue cia/aiiy
(CN) o aeniei/anoioio ae?eyieo niaeo?a. Aiaeia?/ia ci?uaiiy
niinoa??aa?oueny aeey eiiieaen?a c i-ai?ceaeeiii, i-enee?aeeiii oa
2-iaooeeai?iii, a oaeiae a ?yaeao i??acieii?a oa a?ae?aceae?a ea?aiiiaeo
eeneio. Aaee/eia aaeaioieo eieeaaiue (Nwmetafile8? ??‰????????????
???????????yyy????.????1?????? ???????
@????&??yyyy?????Ayyy0???@??p?? ???&?
?MathType??????u@th?????? Oe?eaai i?ine?aeeoaaoe, ye ci?ith?oueny
iieiaeaiiy /anoioe aaeaioieo eieeaaiue oe?aiia?oi (CN) a?ae aaee/eie
iioaioe?ae?a eii?caoe?? i?aai?/ieo ai?i?a, ye? aoiaeyoue a ii??aee
eao?ii (?en.5).

A ?yaeo aea/aieo eiiieaen?a iaia? /?oei? caeaaeiino? aaee/eie (CN) a?ae
iioaioe?aeo eii?caoe?? i?aai?/ieo ai?i?a. Ia cia/aiiy aaee/eie (CN) a
a?eueo?e i??? aieeaa? i?e?iaea Iaoae?a-eiiieaeniooai?thaa/?a.

A oie aea /an aeey oe?ai?aeieo eiiieaen?a Oa?oio, ?ooai?th oa
Iie?aaeaio c iai?aai?/ieie eao?iiaie niinoa??aa?oueny /?oea caeaaei?noue
aaee/eie (NN) a?ae eiiieo ?aae?on?a aai iioaioe?a?e?a eii?caoe??
ciai?oiueinoa?ieo eao?ii?a. I?e/iio, i?e ca?eueoaii? iioaioe?aeo
eii?caoe?? eao?iio a ?yaeao Cs, Li oa Ba, Mg /anoioa aaeaioieo eieeaaiue
oe?aiia?oi c?inoa?. sse ne?aeo? c i?iaaaeaiiai ii??aiyiiy, Acioai?ni?
ii??a? eao?iie ii-?ioiio aieeaathoue ia aaee/eio (CN), i?ae iai?aai?/i?
eao?iie.

Aiae?c ?* niaeo??a oe?ai?aeieo aaeoeo?a M(CN)2L (M = Mn2+, Co2+, Ni2+;
L=DMSO, DMFA, DMAA), Co(CN)2xR3PO (R =CH3, x=1; C2H5, C4H9, C6H5, x=0,5)
oa eiiieaen?a (NH4)2[Co(CN)5L] (L = DMSO, DMFA) iieacaa, ui
eii?aeeiaoe?y e?aaiae?a a ieo a?aeaoaa?oueny /a?ac aoiie Eenith o
aeaeyae? iaeo?aeueieo iieaeoe, i?i ui na?ae/eoue ci?uaiiy a ?* niae?oao
nioa iiaeeiaiiy (S=O), (C=O), (P=O) o iecueei/anoioio ae?eyieo niaeo?a.
E?euee?noue eii?aeeiiaaieo iieaeoe o?eaee?eoino?iieneaeo caeaaeeoue a?ae
?o ?ici???a oa noa?e/iiai oaeoi?o. Iayai?noue o?eueee iaei???
?ioaineaii? nioae iiaeeiaiue (Nwmetafile8? ??‰????????????
???????????yyy????.????1?????? ???????
@????&??yyyy?????Ayyy0???@??p?? ???&?
?MathType??????u@th?????? A ?icae?e? 4 iiaeaii ?acoeueoaoe
aeine?aeaeaiiy e?enoae?/ii? no?oeoo?e o?ueio oeiiaeo i?aaenoaaiee?a
oe?ai?aeieo eiiieaen?a (DH)2[Fe(CN)5NO], (NH4)4[Ru(CN)6],
(NH4)4[Mo(CN)8]0,5I2I.

I?inoi?iaa ?ici?uaiiy eao?ii-ai?ii a ae?aioei??eeiaoai??aiio eiiieaen?
(DH)2[Fe(CN)5NO] (a=1,5701(3), b=1,6034(3), c=1,0496(2) ii, =
110,38(2), ?ic?.=1,34 a/ni3, Z=2, i?inoi?iaa a?oia P21/b) cia?aaeaii ia
?en. 6. A eii?aeeiaoe?eiiio ieoaaae?? aoii?a Oa?oio a?oie NN ? NI
?ici?uai? noaoenoe/ii.

I?e ooai?aii? ae?aioei??eeiaoai??aiai eao?iio (DH+) i?ioii I+
i?e?aeio?oueny aei iaeiiai c ea?aii?eueieo aoii?a Eenith (I(1)) iieaeoee
ae?aioei??eeiaoaio. Aeoiaey/e c i?aeaoiiii? a?aeaeae? i?ioii?ciaaiiai
aoiio Aiaeith c non?aei?i aoiiii Eenith I(2) ea?aii?eueii? a?oie 0,1418
ii, iiaeia noaa?aeaeoaaoe i?i ooai?aiiy i?oeiiai cayceo I(2)…I.

O eao?ii? (DH)+ a?aenooi? a?euei? ea?aii?euei? a?oie, ui
i?aeoaa?aeaeooue aeai? ?* niaeo??a i?i a?aenooi?noue aaeaioieo eieeaaiue
ca’yce?a N=I a oe?ai?aeieo eiiieaenao ae?aioei??eeiaoai?th. Ooai?aiiy
eao?iio ae?aioei??eeiaoai?th aeeeth/a? iiaeeea?noue ooai?aiiy aiaeiaaeo
ca’yce?a H…N i?ae i?ioii?ciaaieie aoiiaie Aiaeith ? aoiiaie Acioo
oe?aiia?oi, ye oea niinoa??aa?oueny eiiieaenieo oe?ai?aeieo eeneioao.
I?inoi?iaa ?ici?uaiiy eao?ii-ai?ii o eiiieaen? (DH)2[Fe(CN)5NO] nooo?ai
a?ae??ciy?oueny a?ae i?inoi?iaiai ?ici?uaiiy eii?a a iai?aai?/ieo nieyo
oe?ai?aeieo eiiieaen?a, aea eao?ii iaoaeo ciaoiaeeoueny o aaciina?aaei?e
aeecueeino? a?ae aoii?a Acioo oe?aiia?oi, ia yeeo cina?aaeaeaii
a?ae’?iiee ca?yae ai?iio. I?e oeueiio eiaeiee eao?ii ciaoiaeeoueny a
na?aaeei? iiiaia?aiieea, aa?oeiaie yeiai ? aoiie Acioo oe?aiia?oi. Aeey
ii??aeo nieae oe?ai?aeieo eeneio oaea aaiiao??y ioi/aiiy i?aai?/iiai
eao?iio aeeeth/a?oueny /a?ac noa?e/i? oneeaaeiaiiy. Aeoiaey/e c
no?oeoo?e (DH)2[Fe(CN)5NO], ii??a? nie? oe?ai?aeieo eeneio iiaeia
?icaeyaeaoe ye oeiia? nie? c ca’yceaie eao?ii-ai?ii ca aeiiiiiaith
aeaeo?inoaoe/ieo nee i?eoyaaiiy. Cia/aiiy i?aeaoiiieo a?aeaeaeae aoii
Acioo oe?aiia?oie – iaeaeeae/? aoiie ae?aioei??eeiaoai?th a e?enoaeao
(DH)2[Fe(CN)5NO] ia?aaeuothoue cia/aiiy aeiaaeei o?i?/ieo oa
Aai-aea?-Aaaeuen?anueeeo ca’yce?a.

Niieoea (NH4)4[Ru(CN)6] e?enoae?co?oueny a o?eaiiaeuei?e neiaii??:
i?inoi?iaa a?oia Pwmetafile8? ??!????????????
???????????yyy????.????1?????? ???????
@ ???&??yyyy?????Ayy`i ???&? ?MathType?? ?
???u?????????»????-?????[?@????[?P???uay??????Aeayeee
aeao?oeeo eao?ii?a aiii?th a no?oeoo?? aeaco? ia oa, ui /anoeia aoii?a
?ooai?th ciaoiaeeoueny a nooiai? ieeniaiiy, aeu?e i?ae +2. Oea,
i/aaeaeii, i?eaiaeeoue aei e?enoaeia?ao?/ii? aeeoa?aioe?aoe?? aoii?a
?ooai?th a aeine?aeaeoaai?e no?oeoo??. Oiio ai?iie [Ru(1)(CN)6]2-
ioi/ai? o?ueiia eao?iiaie aiii?th, a [Ru(2)(CN)6]2- — /ioe?ia ?
ciaoiaeyoueny a na?aaeei? o?eaiiaeueii? i??ai?aee, a aa?oeiao yei?
?ici?uai? eao?iie aiii?th. Aaenaoe?aii?ooaiao-ai?iie iiaoaeiaai?
aeineoue neiao?e/ii — oea aeaui niethuai? ie?aaae?e neiao???
wmetafile8? ??§????????????
???????????yyy????.????1?????? ???????
a@???&??yyyy?????Ayyy°yyy??? Niieoea (NH4)4[Mo(CN)8]0,5H2O
e?enoae?co?oueny a ?iia?/i?e neiaii?? (i?inoi?iaa a?oia Pma2,
a=1,5550(3), b=1,4118(3), c=0,7438(1) ii, Z=4) (?en. 8).

Aoiie Iie?aaeaio a no?oeoo?? (NH4)4[Mo(CN)8]0,5H2O, ye? caeiathoue aeaa
ie?ai? iieiaeaiiy 2(b) ? 2(c), ioi/ai? eiaeiee a?nueiiia oe?ai?aeieie
e?aaiaeaie. Eii?aeeiaoe?ei?e noa?? Mo(1) a?aeiia?aea? aeiaeaeaaae? c
?aeeiith a?nnth neiao??? 2, a eii?aeeiaoe?eiei iiiaia?aiieeii aoii?a
Mo(2) ? aioei?ecia neiao??? m.

A?aenoai? Acio oe?aiia?oie — aiii?e ? a iaaeao 0,282-0,356 ii, ui aeaco?
ia ?nioaaiiy aiaeiaaeo ca’yce?a Nwmetafile8? ??‰????????????
???????????yyy????.????1?????? ???????
@????&??yyyy?????Ayyy0???@??p?? ???&?
?MathType??????u@th?????? A ?yae? niieoe (NH4)4[Mo(CN)8]0,5H2O,
K4[Mo(CN)8]2H2O, Rb4[Mo(CN)8]3H2O e?euee?noue iieaeoe e?enoae?caoe?eii?
aiaee ia iaeio oi?ioeueio iaeeieoeth ieoaoe?aiiiie?aaeaoo c?inoa?. Oey
ianoaaeia i?eaiaeeoue aei cia/ii? ??cieoe? a e?enoae?/ieo no?oeoo?ao
?icaeyaeoaaieo eiiieaen?a, oi/ ?ici??e eao?ii?a (rNH4+=0,143, rK+=0,133,
rRb+= 0,149 ii) ia aeeeth/aee iiaeeeai? ?cino?oeoo?iino? oeeo
eiiieaen?a. Oae, K4[Mo(CN)8]2H2O ? (NH4)4[Mo(CN)8]0,5H2O, ye?
e?enoae?cothoueny a ?iia?/i?e neiaii??, a?ae??ciythoueny i?ae niaith ia
o?eueee neiao???th aeaiaioa?ieo eii??ie, aea ? ??cieie oeiaie
eii?aeeiaoe?eieo iie?aae??a iie?aaeaio: ieiueiiee aeiaeaeaaae? a
eae??ai? nie?, a aiii?ei?e — inueiaee aeiaeaeaaae? oa aioei?ecia. A oie
aea /an eiiieaen Rb4[Mo(CN)8]3H2O e?enoae?co?oueny a oao?aaiiaeuei?e
neiaii??, a ai?ii ia? eii?aeeiaoe?th aen?aeueiiai aeiaeaeaaae?a.
Iaea?aeai? ?acoeueoaoe aeia?a ocaiaeaeothoueny c eiioeaioe??th Oi?aea ?
N?eueaa?oiia i?i aeii?ioth/o ?ieue ci?ie aaee/eie aia?a??
oe?aiie?aaiaeii? aca?iiae?? i?e ooai?aii? iaaiiai eii?aeeiaoe?eiiai
iie?aae?a a iie?oe?ai?aeieo ai?iiao.

A ?icae?e? 5 ?icaeyiooi iniaeeaino? oa?iie?co oe?ai?aeieo eiiieaen?a
ia?ao?aeieo iaoae?a c niieoeaie, ui i?noyoue Acio ? Eenaiue.

A oiae? ocaaaeueiaiiy aenia?eiaioaeueieo aeaieo anoaiiaeai? oae?
iniiai? caeiiii??iino? oa?iie?co oe?ai?aeieo eiiieaen?a ia?ao?aeieo
iaoae?a c N, I-ai?nieie ii??aeie eao?iiaie. Iine?aeiai?noue oa i?e?iaea
o?ceei-o?i?/ieo ? no?oeoo?ieo ia?aoai?aiue, ui noi?iaiaeaeothoue
oa?i?/iee ?iceeaae oe?ai?aeieo eiiieaen?a, iathoue ye ni?euei?, oae ?
a?aei?ii? iniaeeaino?.

Oa?iie?c a?aeaoaa?oueny nooi?i/aoi. Ia?oa noaae?y a?aeiia?aea?
aeaeaeaiith iieaeoe e?enoae?caoe?eii? aiaee. Aeaa?ae?aoaoe?y eiiieaen?a
i?ioiaeeoue ca iaa?ae?ie?oe/iei iaoai?ciii ? ia noi?iaiaeaeo?oueny
?oeioaaiiyi eiiieaeno. Iecuee? oaiia?aoo?e a?aeuaieaiiy aiaee aeacothoue
ia ?? oeaie?oio oa e?enoae?caoe?eio i?e?iaeo.

Ia ae?oa?e noaae?? ii/eia?oueny ?iceeaae eiiieaen?a. I?e ?iceeaae? a
ia?oo /a?ao i?ioiaeeoue a?aeuaieaiiy ? i??ie?c N-, O-ai?nieo ii??aeo
eao?ii?a. Aeey oe?ai?aeio eiiieaen?a Fe(??) niinoa??aa?oueny /anoeiaee
?iceeaae H4[Fe(CN)6] c aeae?eaiiyi oe?ai?aeo aiaeith.

Ia o?ao?e noaae?? aeey oe?ai?aeieo eiiieaen?a Mo (IV), Fe (III), Co
(III) a?aeaoaa?oueny a?aeiiaeaiiy oeaio?aeueiiai aoiia eiiieaeniiai
ai?iio ca ?aooiie ieeniaiiy /anoeie oe?aiia?oi ca ?aaeoe?yie:

2H4[Mo(CN)8] 2H4[Mo(CN)6]+2(CN)2),

3H3[Fe(CN)6] Fe2[Fe(CN)6] + 9 HCN + 3/2(CN)2.

Ia /aoaa?o?e noaae?? a?aeaoaa?oueny ?iceeaae aaenaoe?aiiaeo eeneio
ia?ao?aeieo iaoae?a c ooai?aiiyi i?inoeo oe?ai?ae?a ca ?aaeoe?yie:

3H4[Fe(CN)6] Fe2[Fe(CN)6] + 12HCN,

H4[M(CN)6] M(CN)2 + 4HCN (M=Ru2+, Mo2+).

Ia i’yoiio aoai? a?aeaoaa?oueny ?iceeaae i?inoeo oe?ai?ae?a c
ooai?aiiyi a?eueieo iaoae?a, ea?a?ae?a iaoae?a ? aoaeaoeth ca
?aaeoe?yie:

Fe2[Fe(CN)6] = 3Fe(CN)2 Fe3C + 5C 3N2,

Fe3C Fe2C + Fe 3Fe + C,

Ru(CN)2 Ru + 2C +N2,

2Mo(CN)2 Mo2C + 3C + 2N2.

Ca ii/aoeiaeie oaiia?aoo?aie oa?iie?co ii??a? oe?ai?aei? eiiieaene
iiaeia ?ici?noeoe a ianooii? ?yaee oa?i?/ii? no?eeino?:

aaenaoe?aiioa?aoe (??): ae?aoeeai?i, o?eaoeeai?i, 1,2,3-aaicio?eacie
(170) > aooeeai?i (165) > 2-ai?iii??eaeei, 2-iaooeeai?i,
iaooeea?ae?aceae, iaooeeaoeaoeea?ae?aceae (160) > ae?aoeeaio?eai?i,
aaenaiaoeeaiae?ai?i, aoeeaiae?ai?i, aaiceeai?i (150),
a?iiaaici?ea?ae?aceae (140) > i-oie?aeei, i-oieo?aeei, 1-iaooeeai?i
(135) > ai?e?i (130) > ooeaaceae (125) > i-enee?aeei, oai?ea?ae?acei,
aoeaoeea?ae?aceae, aaiceaeei (120) > ooaaceae, 4-ai?iiaioei??ei (110) >
i-ai?ceaeei, ai?aeii??ei (100iN);

aaenaoe?aii?ooaiaoe (??): aaiceeai?i (190) > 2-ai?iii??eaeei,
1,2,3-aaicio?eacie (170) > ae?aoeeai?i (165) > ae?aoeeaio?eai?i (160) >
aoeeaiae?ai?i, i-enee?aeei (150) > ai?e?i (140) > i-oieo?aeei (135) >
oai?ea?ae?acei, i-oie?aeei, 2-iaooeeai?i (120) > i-ai?ceaeei (100 iN);

ieoaoe?aiiiie?aaeaoe (IV): i-oie?aeei (150) > aaiceeai?i (140) >
2-ai?iii??eaeei (110) > aoeeaiae?ai?i, 2-iaooeeai?i (100iN).

Oa?iie?c ci?oaii-e?aaiaeieo eiiieaen?a (NH4)2[Co(CN)5L], aea L-DMSO,
DMFA a?ae??ciy?oueny a?ae oa?iie?co aiiie?aaiaeieo eiiieaen?a
aeiaeaoeiaei aoaiii aeae?eaiiy DMSO, DMFA. Aeine?aeaeaiiy oa?i?/iiai
?iceeaaeo oe?ai?aeieo aaeoeo?a M(CN)2L (M=Mn, Co, Ni; L=DMSO, DMFA,
DMAA) iieacaei, ui a?aeuaieaiiy ? ?iceeaae L i?ioiaeeoue i?e
oaiia?aoo?ao 200-400iN, ye? cia/ii aeu? oaiia?aoo? eei?iiy a?aeiia?aeieo
e?aaiae?a. Oea i?aeoaa?aeaeo? ?nioaaiiy a oe?ai?aeieo aaeoeoao M(CN)2L
i?oeiiai ca’yceo M-L.

Ia ?en. 9 cia?aaeaii caeaaei?noue oaiia?aoo?e ii/aoeo ?iceeaaeo
(tii/.), oaiia?aoo?e iaeneiaeueiiai ?icaeoeo ?aaeoe?? a?aeuaieaiiy oa
i??ie?co i?aai?/ieo eao?ii?a (tS1), oaiia?aoo?e iaeneiaeueiiai ?icaeoeo
?aaeoe?? aeano?oeoe?? i?inoeo oe?ai?ae?a (tS2) a?ae iniiaiino?
i?aai?/ieo ai?i?a, ye? aoiaeyoue a ii??aee eao?ii. sse aeaeii c ?enoie?a
i?ae oeeie oaiia?aoo?aie oa iniiai?noth i?aai?/ieo ai?i?a, ?nio? iaaia
ei?aeyoe?y. Ca oaiia?aoo?aie tii/ ii??a? oe?ai?aei? eiiieaene iiaeia
?icae?eeoe ia aea? a?oie:

1 — eiiieaene c oaiia?aoo?ith ii/aoeo ?iceeaaeo 150-190 iN, ye? i?noyoue
a ii??aiio eao?ii? i?aai?/i? ai?ie, ?Eb yeeo iaioa 5;

2 — eiiieaene c oaiia?aoo?ith ii/aoeo ?iceeaaeo 100-170 iN, ye? i?noyoue
a ii??aiio eao?ii? i?aai?/i? ai?ie, ?Eb yeeo a?eueoa 7.

Oaeei /eiii, oaiia?aoo?a ii/aoeo ?iceeaaeo oe?ai?aeieo eiiieaen?a Oa?oio
(II), ?ooai?th (II), Iie?aaeaio (IV) caeaaeeoue a ia?oo /a?ao a?ae
i?e?iaee ? iniiaiino? ai?i?a a ii??aeo eao?iiao, a a ae?oao — a?ae
i?e?iaee Iaoae?a-eiiieaeniooai?thaa/?a.

Ianooiiei oaeoi?ii — ? iayai?noue a iieaeoeao ai?i?a ??cieo cai?niee?a.
Oea aeia?a aeaeii ia i?eeeaae? oe?ai?aeieo eiiieaen?a Fe (II) a ?yaeo
ai?e?i (130) — i-oieo?aeei (135) — i-enee?aeei (120) — i-ai?ceaeei (100)
— aaiceeai?i (170 iN). Aaaaeaiiy iaei??? a?oie CH3 a iieaeoeo ai?e?io
i?eaiaeeoue aei iacia/ii? ci?ie iniiaiino? i-oieo?aeeio ? aei iacia/iiai
i?aeaeuaiiy tii/.. I?e aaaaeaii? aeaio a?oi CH3 a i-enee?aeei?
iniiai?noue ai?io ciaioo?oueny, ui i?eaiaeeoue aei ciaioaiiy tii/..
Iiyaa aoii?a Eenith a iieaeoe? i-ai?ceaeeio i?eaiaeeoue aei cia/iiai
cieaeaiiy oaiia?aoo?e ?iceeaaeo, a iiyaa a?oie -NI2NH2 a aaiceeai?i?
i?eaiaeeoue aei ??ceiai i?aeaeuaiiy oaiia?aoo?e aei 170 iN.

I?e aea/aii? i?ioean?a oa?i?/iiai ?iceeaaeo oe?ai?aeieo eiiieaen?a
Oa?oio (II) ? ?ooai?th (II) c 2-ai?iii??eaeeiii, oai?ea?ae?aceiii ?
1,2,3-aaicio?eacieii anoaiiaeaii aieea ia tii/. oa tS1 aeiaeaoeiaeo
i?ioiiiaeoeaioi?ieo a?oi, ye? ? a iieaeoeao iacaaieo ?a/iaei.

Aaenaoe?aiioa?aoe (??), -?ooaiaoe (??) 2-ai?iii??eaeei?th iathoue
cia/ii aeu? oaiia?aoo?e ii/aoeo oa?iie?co, i?ae c ?ioeie i?aai?/ieie
ai?iaie. Oea, i/aaeaeii, ca’ycaia c oei, ui a iieaeoe? 2-ai?iii??eaeeio
? aeiaeaoeiaee i?ioiiiaeoeaioi?iee oeaio?, yeee ni?ey? neeuei?oiio
ca’yceo eiai c a?aeiia?aeieie eeneioaie. Oea i?eaiaeeoue aei ?inoo
oa?i?/ii? no?eeino? eiiieaen?a. Oai?ea?ae?acei a aieiaiio eaioethao
i?noeoue a?oio NHNH2. A?oia NH ? «cae?eoith» ? iaeaea ia aieeaa? ia
no?ee?noue eiiieaen?a. Oiio aaenaoe?aiioa?aoe (??) ? -?ooaiaoe (??)
oai?ea?ae?acei?th iathoue tii/. oae? ae , ye eiiieaene c ai?e?iii ? eiai
iio?aeieie. Aieea aeiaeaoeiaeo i?ioiiiaeoeaioi?ieo a?oi aeia?a aeaeii ia
oe?ai?aeieo eiiieaenao Oa?oio (II) ? ?ooai?th (II) c
1,2,3-aaicio?eacieii, a iieaeoe? yeiai ? o?e i?ioiiiaeoeaioi?i? oeaio?e.
Iniiai?noue aaicio?eacieo (pKb=12,4) iaaaaaoi ieae/a a?ae iniiaiino?
2-ai?iii??eaeeio ? iiaeia aoei a i/?eoaaoe ??ceiai cieaeaiiy oaiia?aoo?e
ii/aoeo ?iceeaaeo, iaeiae, a ii??aithaaieo niieoeao aiie iathoue
aeecuee? ii/aoeia? oaiia?aoo?e ?iceeaaeo, ui na?ae/eoue i?i cia/iee
aieea aeiaeaoeiaeo i?ioiiiaeoeaioi?ieo a?oi ia oa?i?/io no?ee?noue
eiiieaen?a.

sseui c oi/ee ci?o aeyaeaieo caeiiii??iinoae i?iaiae?coaaoe no?ee?noue
eiiieaen?a a ?ioeo ?yaeao, oi aa/eii, ui aiie ni?aaaeaeothoueny ? aeey
ieo. Oae, oa?ioe?ai?aei? eiiieaene c aaiceaeeiii (120 iN) ? i-oie?aeeiii
(135 iN) i?aeoaa?aeaeothoue iieiaeaiiy, ui aaaaeaiiy cai?niee?a a yae?i
i?eaiaeeoue aei ci?ie oaiia?aoo?e ii/aoeo oa?iie?co. Aeey eiiieaen?a c
1-iaooeeai?iii (135 iN) oa 2-iaooeeai?iii (160 iN) ci?ia iieiaeaiiy
ai?iia?oie i?eaiaeeoue aei i?aeaeuaiiy oaiia?aoo?e ii/aoeo ?iceeaaeo.

A ?yae? eiiieaen?a c a?ae?aceaeaie ea?aiiiaeo eeneio i?e ci?i? i?e?iaee
iniiaiiai eaioethaa ci?ith?oueny oaiia?aoo?a ii/aoeo oa?iie?co. C
oneeaaeiaiiy eaioethaa oey oaiia?aoo?a i?aeaeuo?oueny. A ?yae?
oe?ai?aeieo eiiieaen?a c 4-ai?iiaioei??eiii, ai?aeii??eiii, aiaeuea?iii
i?e oneeaaeiaii? no?oeoo?e a?aeaoaa?oueny cieaeaiiy oaiia?aoo?e ii/aoeo
?iceeaaeo. Ca oa?i?/iith no?ee?noth, a caeaaeiino? a?ae i?e?iaee
Iaoaeo-eiiieaeniooai?thaa/a, ii??a? oe?ai?aei? eiiieaene iiaeia
?ici?noeoe a ?yae Ru>Fe>Mo (ca tS1), Fe>Ru>Mo (ca tS2).

Ia iniia? oa?iia?aa?iao?e/iiai aeine?aeaeaiiy oe?ai?aeieo eiiieaen?a Fe
(II), Ru (II), Mo (IV) c i?aai?/ieie N-ai?nieie eao?iiaie i?iaaaeaii
iaoaiaoe/io ia?iaeo ?acoeueoao?a AeOA ia?cioa?i?/iei ?ioaa?aeueiei
iaoiaeii Oi?ia?oea-Iaoeaa?a. ?acoeueoaoe ?ic?aooieo e?iaoe/ieo
ia?aiao??a aeey aoaio oa?i?/iiai ?iceeaaeo ii??aeo eao?ii?a oe?ai?aeieo
eiiieaen?a Oa?oio, ?ooai?th oa Iie?aaeaio iiaeaii a oaaeeoe? 1.

sse aeaeii c oaaeeoe? 1, a ?yaeo aaenaoe?aiioa?ao?a (??), ye? i?noyoue o
ciai?oi?e noa?? ae?oaoe/i? ai?ie, aia?a?y aeoeaaoe?? ci?ith?oueny a
?yaeo: ia?aeiiee (aooeeai?i), aoi?eiiee (ae?aoeeai?i), o?aoeiiee
(o?eaoeeai?i) ai?i, ui na?ae/eoue i?i oa, ui no?ee?noue eiiieaen?a
caeaaeeoue a?ae i?e?iaee ? aoaeiae ciai?oiueinoa?ieo eao?ii?a. Cai?ia
ai?e?io ia i-enee?aeei, aaiceaeeio ia i-oie?aeei a oe?ai?aeieo
eiiieaenao oaeiae i?eaiaeeoue aei ca?eueoaiiy aia?a?? aeoeaaoe?? oa lgA.

Oaaeeoey 1.

E?iaoe/i? ia?aiao?e i?ioeano oa?i?/iiai ?iceeaaeo ii??aeo eao?ii?a
oe?ai?aeieo eiiieaen?a Fe (II), Ru (II), Mo (IV)

?

i/iNiieoeapKbE,

eAeae/iieueH,
eAeae/iieuelgAL=[Fe(CN)6]4-1[(C2H5)2NH2]4L3,07125,5104,711,92[(C2H5)3NH]
2H2L3,13109,5116,110,03[C4H9NH3]4L3,39100,877,39,04[NH(CH2CH2NH3)2]2L3,9
5106,270,59,15[NH2(CH2)2NH3]4L4,04114,594,39,56[C6H5CH2NH3]4L4,62173,114
6,117,37[C5H4NNH3]4L7,1100,181,78,58[NH2(C6H3)2(CH3)2
NH3]2H2LH2O9,0398,285,29,89[C6H5NH3]4L9,3885,8110,98,310[CH3C6H4NH3]4L2H
2O9,46122,565,612,511[CH3OC6H4NH3]4L9,51125,1104,313,212[(CH3)2C6H3NH3]4
LH2O9,6292,987,510,413[2-C10H7NH3]4L9,8118,897,411,114[1-C10H7NH3]4L10,0
118,394,811,015[NH2(C6H4)2NH3]3HL10,2566,852,75,116[C6H4N2NH2]2H2L12,480
,4111,76,8L=[Ru(CN)6]4-1[(C2H5)2NH2]4L2H2O3,07147,8120,913,84[NH(CH2CH2N
H3)2]2L2H2O3,95128,272,410,65[NH2(CH2)2NH3]2H2L4,04121,886,09,66[C6H5CH2
NH3]4L4,62213,9132,619,17[C5H4NNH3]4L7,1122,1123,610,68[NH2(C6H3)2(CH3)2
NH3]2H2LH2O9,03107,874,010,49[C6H5NH3]4L9,38134,2133,012,510[CH3C6H4NH3]
4L4H2O9,46109,067,819,111[CH3OC6H4NH3]4L9,51143,253,116,112[(CH3)2C6H3NH
3]2H2L
H2O9,62160,8138,015,513[2-C10H7NH3]4L9,8106,7104,19,7L=[Mo(CN)8]4-8[NH2(
C6H3)2(CH3)2NH3]2

H2L4H2O9,03107,271,011,213[2-C10H7NH3]4L8H2O9,893,582,89,5

Oa?aeoa? ci?ie e?iaoe/ieo ia?aiao??a o oe?ai?aeieo eiiieaenao Oa?oio ?
?ooai?th c N-ai?nieie ii??aeie eao?iiaie iiae?aiee, o?eueee eiiieaene
?ooai?th iathoue oe? cia/aiiy aeaui aeu?, i?ae eiiieaene Oa?oio.

E?iaoe/i? ia?aiao?e ci?iththoueny a caeaaeiino? a?ae i?e?iaee ai?i?a,
ui aoiaeyoue a ii??a? eao?iie oa Iaoae?a-eiiieaeniooai?thaa/?a.
Eiiieaene, ye? i?noyoue ai?ie c ?Eb=9-12, iathoue ieae/? cia/aiiy
aia?a?? aeoeaaoe??. Ia ?en. 11 iiaeaii caeaaei?noue lgA a?ae aia?a??
aeoeaaoe?? aeey ii??aeo oe?ai?aeieo eiiieaen?a Oa?oio ? ?ooai?th. Oey
caeaaei?noue ia? e?i?eiee oa?aeoa?, ui na?ae/eoue i?i iayai?noue
eiiiainaoe?eiiai aoaeoo.

?yaee, neeaaeai? a ii?yaeeo ciaioaiiy aia?a?? aeoeaaoe??, ia
ni?aiaaeathoue c ?yaeaie, neeaaeaieie a ii?yaeeo ciaioaiiy oaiia?aoo?e
ii/aoeo oa?iie?co eiiieaen?a.

I?ioeane aeaa?ae?aoaoe?? an?o a?ae?aoiaaieo eiiieaen?a a?aeaoaathoueny a
iaaeao oaiia?aoo? 60-130 iN ? iathoue aeecuee? cia/aiiy aia?a??
aeoeaaoe?? a iaaeao 50-70 eAeae/iieue, ui aeaco? ia e?enoaeia?ae?aoio
i?e?iaeo aiaee.

A ?icae?e? 6 aeine?aeaeaii aieea ai?ioiiieo ?ic/eiiee?a ia oiiae
neioaco, aeanoeaino? oa ?aaeoe?eio caeaoi?noue oe?ai?aeieo eiiieaen?a.
Iieacaii, ui a na?aaeiaeu? ai?ioiiieo ?ic/eiiee?a (DMSO, DMFA, DMAA),
aeei?enoiaoth/e

aeia?a ?ic/eiiee a ieo oe?ai?ae aiii?th, iiaeia iaea?aeaoe
ianieueaaoiaai? aai nieueaaoiaai? oe?ai?aee, ye? iaiiaeeeai iaea?aeaoe o
aiaeieo ?ic/eiao. Oae, c aeeiaoeeoi?iai?aeiiai ?ic/eio oei?eaeo aai
aoeaoaoo oeeieo aeae?eaii Zn(CN)2, c aeeiaoeenoeueoieneaeii? noniaic??
oei?eaeo iaeaae?th — Pd(CN)2, a c na?aaeiaeua ai?ioiiieo ?ic/eiiee?a
aeae?eaii oe?ai?aei? aaeoeoe M(CN)2L, L = DMSO, DMFA, DMAA. Aeaia
iaoiaeeea aeicaiey? iaea?aeoaaoe oe?ai?aee aeniei? /enoioe, a
aeei?enoaiiy aaciiiae?aiiai oe?ai?aeo aiii?th, ye oe?aioth/iai aaaioo,
aeeeth/a? ooai?aiiy iia?/ieo i?iaeoeo?a ?iceeaaeo oe?ai?ae-?ii?a,
a?ae?ie?c eiiieaen?a. Aiia iiaea aooe ?aeiiaiaeiaaia aeey neioaco ?ioeo
oe?ai?aeieo eiiieaen?a.

I?e aeaeueoiio oe?aioaaii? M(CN)n oe?ai?aeii aiii?th a na?aaeiaeu?
ai?ioiiieo ?ic/eiiee?a iiaeia iaea?aeaoe aiii?ei? nie? oe?ai?aeieo
eeneio (NH4)2[Co2(CN)10]3DMFA, (NH4)2[Ni(CN)4], (NH4)2[Pd(CN)4] 3DMSO,
ye? iaiiaeeeai iaea?aeaoe o aiaeieo ?ic/eiao /a?ac a?ae?ie?c NH4CN ?
iaea?aeoaaiiai eiiieaeno.

??cieoey a aeaeo?iiiaeiii?i?e caeaoiino?, ae?aeaeo?e/i?e i?iieeeeaino?
ai?ioiiieo ?ic/eiiee?a ? aiaee aieeaa? ia aeanoeaino? oe?ai?aeieo
eiiieaen?a a oeeo na?aaeiaeuao. A ia?oo /a?ao oea niinoa??aa?oueny a
aeaeo?iiieo niaeo?ao oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a.
Iacaeaaeii a?ae aoaeiae oe?ai?aeiiai eiiieaeno, nooiaiy ieeniaiiy
Iaoaeo-eiiieaeniooai?thaa/a niinoa??aa?oueny ci?uaiiy oa?aeoa?enoe/ieo
nioa iiaeeiaiiy a aeiaaioaeeueiao ae?eyieo niaeo?o a ai?ioiiieo
?ic/eiieeao o ii??aiyii? c aiaeieie ?ic/eiaie. Oeae cnoa aeia?a aeaeii
ia eiiieaenao [Ni(CN)4]2-, [Co(CN)6]3-, [Mo(CN)8]4- o aiaeieo ?
aeeiaoeenoeueoieneaeieo ?ic/eiao (oaae. 2). Iaea?eueoa ci?uaiiy
niinoa??aa?oueny aeey [Mo(CN)8]4—ai?iio. Aaeeea eii?aeeiaoe?eia /enei a
oeueiio eiiieaen? ia iiaea aooe i?e/eiith oaeiai ci?uaiiy
oa?aeoa?enoe/ieo nioa iiaeeiaiiy o ii??aiyii? c eiiieaenaie [Ni(CN)4]2-
? [Co(CN)6]3- , ine?eueee ia?ao?ae a?ae eii?aeeiaoe?eiiai /enea 4 aei 6
ia i?eaiaeeoue aei cia/ieo a?aei?iiinoae max aiaeieo ?
aeeiaoeenoeueoieneaeieo ?ic/ei?a. Ia oea ci?uaiiy oaeiae iaei aieeaa? ?
nooi?iue ieeniaiiy Iaoaeo-eiiieaeniooai?thaa/a. Iaea?eueo eiia??ii ia
oea ci?uaiiy aieeaa? i?oei?noue ca’yceo I-N a eiiieaenao. Aeiaaeeia
ca’yceo Ii-N a [Mo(CN)8]4-, ??aia 0,216 ii, cia/ii a?eueoa a?ae
aeiaaeeie ca’yce?a Ni-C (a [Ni(CN)4]2- 0,186 ii) ? Ni-N (a [Co(CN)6]3-
0,189 ii). Oiio aca?iiae?y i?ae oe?ai?aeieie e?aaiaeaie ? iieaeoeaie
?ic/eiieea a eiiieaen? [Mo(CN)8]4- iiaeiia aooe neeuei?oa, i?ae a
eiiieaenao [Ni(CN)4]2- ? [Co(CN)6]3- .

Oaaeeoey 2

Oa?aeoa?enoe/i? nioae iiaeeiaiiy aeaeo?iiieo niaeo??a aiaeieo ?
aeeiaoeenoeueoieneaeieo ?ic/ei?a oe?ai?aeieo eiiieaen?a Ni(II),
Co(III), Mo(IV).

Eiiieaeniee ai?iimax.,
iiH2ODMSO[Ni(CN)4]2-268,285276,292[Co(CN)6]3259,310262,316[Mo(CN)8]4-368
394

Aeeiaoeenoeueoieneaeia ? aeeiaoeeoi?iai?aeia na?aaeiaeua aieeaathoue ia
aeanoeaino? oe?ai?aeieo eiiieaen?a, i?aeaeuoth/e ?o no?ee?noue o oeeo
?ic/eiieeao. Oea iaeei ?c ni?eueieo i?iya?a aieeao iaaiaeiiai
na?aaeiaeua ia iiaaae?ieo oe?aiiiaoaeao?a. Iai?eeeaae, ye a?aeiii c
aeaieo e?oa?aoo?e, [Co(CN)5]3—ai?ii o aiaeiiio ?ic/ei? oaeaeei noa???
ca ?aaeoe??th

2[Co(CN)5]3-+2H2O = [Co(CN)5H]3-+[Co(CN)5H2O]2-+OH-,

a a aeeiaoeenoeueoieneaeieo ?ic/eiao — no?eeee /a?ac a?aenooi?noue
a?ae?ie?co.

O aiaeieo ?ic/eiao [Co(CN)5]3—ai?ii anooia? oaeiae a ?aaeoe??

2[Co(CN)5]3-+H2 = 2[Co(CN)5H]3-,

2[Co(CN)5]3-+O2 = [(NC)5CoOOCo(CN)5]6-.

A na?aaeiaeu? aeeiaoeenoeueoieneaeo ooai?aiiy a?ae?eaeiiai [Co(CN)5H]3-
eiiieaeno ia a?aeaoaa?oueny, ui iiynith?oueny ia??aiioe?ii?noth
oe?aiia?oi a eiiieaen?, coiiaeaiith ieineii??ai?aeaeueiith aoaeiaith
[Co(CN)5]3—?ii?a. A i?ioeaaao oeueiio ooai?th?oueny eiiieaen
[Co(CN)5DMSO]3-. Aeeiaoeenoeueoieneae ia?aoeiaeaea? i?ioeano ooai?aiiy
ca’yceo Ni-I a ?aaeoe?? a?ae?oaaiiy oa ia iiaea aooe aeei?enoaiee ye
na?aaeiaeua aeey eaoae?oe/iiai a?ae?oaaiiy eiiaie [Co(CN)5]3-. A oie aea
/an, ye aoei iieacaii iaie, nooo?aiai aieeao aeeiaoeenoeueoieneaeiiai
na?aaeiaeua ia ae?oao ?aaeoe?th aca?iiae?? [Co(CN)5]3- c eeniai a
ii??aiyii? c aiaeiei ia niinoa??aa?oueny ? aeo?ae aeeeeniaaiai aaeoeoo
caeaaeeoue a?ae oaiia?aoo?e.

Aeey neioaco iiaeo ci?oaii-e?aaiaeieo oe?ai?aeieo eiiieaen?a o
iaaiaeiiio na?aaeiaeu? aeei?enoaii ?aaeoe?? oioie?co, ii?ii?iaiiy
aeo?aeiiai eiiieaeno OO na?oeii. Oae, a i?ioean? oioie?co aiaeiiai
?ic/eio ieoaoe?aiiiie?aaeaiiai? (IV) eeneioe a?aeaoaa?oueny ooai?aiiy
eiio (aeai)aaioaoe?aiiiie?aaeaoo (IV) [Mo(CN)7H2O]3-, a
aeeiaoeenoeueoieneaeiiai — i?ioiaeeoue oioie?oe/ia ooai?aiiy
(aeeiaoeenoeueoieneae)aaioaoe?aiiiie?aaeaoo (IV) [Mo(CN)7DMSO]3-. Oeae
eiiieaen aeae?eaii o aeaeyae? nie? n??aea Ag3[Mo(CN)7DMSO]. I?i
iayai?noue eii?aeeiiaaiiai aeeiaoeenoeueoieneaeo na?ae/eoue ci?uaiiy
nioae iiaeeiaiiy aaeaioieo eieeaaiue ca’yceo S=O a?ae 1055 ni-1 aeey
a?eueiiai aeeiaoeenoeueoieneaeo aei 1022 ni-1 aeey iaea?aeaiiai
(aeeiaoeenoeueoieneae)aaioaoe?aiiiie?aaeaoo (IV) n??aea. I?e oioie?c?
ieoaoe?aiiiie?aaeaoo (IV) ia noaae?? ooai?aiiy aaioaoe?aiiiie?aaeaoo
iii?oiiai aieeao aeeiaoeenoeueoieneaeiiai na?aaeiaeua, a ii??aiyii? c
aiaeiei, ia aeyaeaii. Iaeiae, oeae aieea i?iyaey?oueny ia ?aaeoe?ei?e
caeaoiino? aaioaoe?aiiiie?aaeaoiiai eiio o ii??aithaaieo na?aaeiaeuao. O
aiaeiiio na?aaeiaeu? (aeai)aaioaoe?aiiiie?aaeao (IV) caeaoiee anooiaoe a
?aaeoe?? e?aaiaeiiai iai?io c iaeeoeii eii?a e?aaiaeo O (O = Cl-, Br-,
NCS-). Ia aeaeo?iiieo niaeo?ao oeae i?ioean oa?aeoa?eco?oueny cieeiaiiyi
nioae iiaeeiaiiy i?e 512 ii ? iiyaith iaeneioio iiaeeiaiiy i?e 476, 488,
428 ii, coiiaeaiiai aeiaeaaaiiyi Cl-, Br-, NCS-, a?aeiia?aeii. Oea
na?ae/eoue i?i i?io?eaiiy o aiaeiiio ?ic/ei? ?aaeoe??:

[Mo(CN)7H2O]3- + X- = [Mo(CN)7X]4- + H2O.

Aiaeia?/i? ?aaeoe?? (aeeiaoeenoeueoieneae)aaioaoe?aiiiie?aaeaoo (IV) c
e?aaiaeaie O a aeeiaoeenoeueoieneaeiiio ?ic/ei? ia i?io?eathoue, ui
aeaco? ia cieaeaiiy o?i?/ii? aeoeaiino? oeueiai eiiieaeno a na?aaeiaeu?
DMSO.

A ?icae?e? 7 iiaeaii ?acoeueoaoe aeine?aeaeaiiy ?ia?aoth/eo
aeanoeainoae oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a.

Aioeei?ic?ei? aeanoeaino? oe?ai?aeieo eiiieaen?a aecia/aee ca
oaeaee?noth ei?ic?? oa nooiaiai caoenoo noaeueieo c?ace?a a?aa?iao?e/iei
iaoiaeii.

Aeey aeine?aeaeaiiy aeei?enoiaoaaee noaeue 40O (caaa?oiaaia, iecueeee
a?aeione), iaeo?aeueia na?aaeiaeua (3%-iee ?ic/ei oei?eaeo iao??th), /an
aei?iaoaaiue — 120 aiaeei, eiioeaio?aoe?y ?ia?a?oi??a — 110-3 — 510-3
iieue/e.

Iaee?au? caoeni? aeanoeaino? iathoue aaenaoe?aiioa?ao (??)
i-ai?iioaiie?th, ieoaoe?aiiiie?aaeao (?V) ae?aoeeaiii?th,
aaenaoe?aiioa?ao (??) 2-ai?iii??eaeei?th, i?o?iciiaioaoe?aiioa?aoe (??)
i?ii?e- oa aaeneeae?aioei??eeiaoai?th oa ieoaoe?aiiiie?aaeao (?V)
aaeneeae?aioei??eeiaoai?th.

Iayai?noue ?ia?aoth/iai aoaeoo i?aeoaa?aeaeaii ?acoeueoaoaie
?iiaaeainieo aeine?aeaeaiue. I?enooi?noue a ei?ic?eiiio na?aaeiaeu?
aaenaoe?aiioa?ao?a (??) i-ai?iioaiie?th, 2-ai?iii??eaeei?th oa
ieoaoe?aiiiie?aaeaoo (IV) ae?aoeeaiii?th i?eaiaeeoue aei cieaeaiiy
i?i?ioia aeeoa?aioe?eii? ?iiino? oa ?icoe?aiiy ae?aiaciio iioaioe?ae?a a
?ia?aiaaiiio ?ic/ei? o ii??aiyii? c ia?ia?aiaaiei (?en. 12). Ci?uaiiy
noaoe?iia?iiai iioaioe?aeo ei?ic?? noae? a ?ia?aiaaiiio ?ic/ei? a a?e
aeiaeaoi?o cia/aiue aeaco? ia oa, ui iacaai? eiiieaene ? ?ia?aoi?aie
ianeaoth/i? ae??. Aeine?aeaeaiiy ei?ic?eii? no?eeino? oa aeiaaia?/iino?
noae? a oiiaao iaeioeeeeiai? aoiie iieacaei, ui aaenaoe?aiioa?ao (??)
2-ai?iii??eaeei?th ? oaeiae aoaeoeaiei ?ia?a?oi?ii ei?ic?eii-aoiiiiai
?oeioaaiiy (?en. 13).

Aeine?aeaeaiiy aaeoa?ioeeaeii? aeoeaiino? oe?ai?aeieo eiiieaen?a ia
anioe?aoeai?e eoeueoo?? aaeoa??e, yea aeeth/a? aoeeaeioiai? o?iiia?
aaeoa??? Thiobacillus thioparus oa noeueoao?aaeoeoth/? Desulfovibrio sp.
iieacaei, ui i?o?iciiaioaoe?aiioa?ao (??) i?ii?eae?aioei??eeiaoai?th
(C26H30N4O2H)2[Fe(CN)5NO], i?o?iciiaioaoe?aiioa?ao (??)
aaeneeae?aioei??eeiaoai?th (C29H36N4O4H)2[Fe(CN)5NO] oa
ieoaoe?aiiiie?aaeao (IV) aaeneeae?aioei??eeiaoai?th
(C29H36N4O2H)4[Mo(CN)8] iathoue oi?io? ?ia?aoth/? oa aaeoa?ioeeaei?
aeanoeaino?. Aiie i?iyaeythoue aaeoa??inoaoe/iee aoaeo, oiaoi ia
cieuothoue i?e?ii?aai?cie, a eeoa i?eai?/othoue ?o ??no. Caaaeyee
?ic/eiiino? a i?aai?/ieo ?ic/eiieeao ?o iiaeia aeei?enoiaoaaoe ye
aioeei?ic?ei? aeiaaaee aei eaeioa?aiaeo iaoa??ae?a.

Aeine?aeaeai? niieoee iathoue aeeo?eueio i?e?iaeo, coiiaeaio iayai?noth
a?ae?ioiaii? (i?aai?/iee eao?ii) ? a?ae?io?eueii? (eiiieaeniee ai?ii)
neeaaeiaeo. Iayai?noue a?ae?ioiaii? /anoeie coiiaeth? ?ic/eii?noue
eiiieaen?a a ?yae? i?aai?/ieo ?ic/eiiee?a, ye? aeei?enoiaothoueny i?e
i?eaiooaaii? eaeioa?aiaeo eiiiiceoe?e. Iayai?noue a?ae?io?eueiiai
eiiieaeniiai ai?iio coiiaeth? ?ic/eii?noue eiiieaen?a o aiae?, ui
aeicaiey? aaiaeeoe ?o o aiaei?ic/eii? eaeioa?aia? iaoa??aee. I?aai?/iee
eao?ii coiiaeth? a?ae?ioia?caoe?th iiaa?oi? iaoaeo, aioeei?ic?ei? oa
aioeaaeoa??aeuei? aeanoeaino? niieoe. Eiiieaeniee ai?ii caaacia/o?
i?ioeei?ic?eiee aoaeo aiane?aeie ooai?aiiy c eiiaie iaoaeo, yeee
ei?iaeo?, iaei?ic/eiieo eiiieaenieo nieae;

Oaeei /eiii, aaenaoe?aiioa?aoe (??) 2-ai?iii??eaeei?th oa
i-ai?iioaiie?th, i?o?iciiaioaoe?aiioa?aoe (??) i?ii?e- ?
aaeneeae?aioei??eeiaoai?th, ieoaoe?aiiiie?aaeao (IV),
aaeneeae?aioei??eeiaoai?th iiaeia ?aeiiaiaeoaaoe aeey i?iieneiaiai
aeei?enoaiiy, aaaaeaiiyi ?o a eaeioa?aia? iie?eooy, ye?
aeei?enoiaothoueny a oiiaao ii?nueei? ei?ic?? oa a?iia?inoaiiy, a
aaenaoe?aiioa?aoe (??) 2-ai?iii??eaeei?th oa i-ai?iioaiie?th iiaeia
?aeiiaiaeoaaoe aeey aioeei?ic?eiiai caoenoo noaeueiiai iaeaaeiaiiy a
caieiooeo nenoaiao iai?ioiiai aiaeiiinoa/aiiy oa a oiiaao
ei?ic?eii-iaoai?/iiai ?oeioaaiiy iaoae?a.

AENIIAEE

1. ?ic?iaeaii o?ceei-o?i?/i? iniiae neioaco iiaeo oe?ai?aeieo eiiieaen?a
ia?ao?aeieo iaoae?a c i?aai?/ieie Eenaiueai?nieie e?aaiaeaie oa Acio- ?
Eenaiueai?nieie eao?iiaie. Neioaciaaii oa aea/aii 89 (aia?oa 80)
oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a c niieoeaie, ui i?noyoue Acio
? Eenaiue o ciai?oi?e ? aioo??oi?e noa?ao. Aia?oa ye oe?aioth/ee aaaio
aeei?enoaii oe?ai?ae aiii?th. Iieacaii, ui aeei?enoaiiy i?e neioac?
iaaiaeieo ?ic/eiiee?a aeeeth/a? a?ae?ie?c, i?aeaeuo? ?ic/eii?noue
eiiieaen?a oa cia/ii ca?eueoo? ?o aeo?ae.

2. Anoaiiaeaii aieea i?e?iaee oeaio?aeueiiai eiio oa e?aaiae?a ia
i?ioeane eiiieaeniooai?aiiy. Noa?aio?i?y ? aoaeiaa neioaciaaieo niieoe
aecia/ai? ca aeaieie ?*- oa aeaeo?iiii? niaeo?ineii??, iaai?oieo
aei??thaaiue, ?aioaaiino?oeoo?iiai aiae?co. Iieacaii, ui
ci?oaii-e?aaiaei? eiiieaene oeio M(CN)2L caa??aathoue iie?ia?io
no?oeoo?o ? eii?aeeiaoe?y e?aaiae?a a?aeaoaa?oueny aiane?aeie
iaaea?aaeaioiino? aoii?a iaoaeo, ye? ciaoiaeyoueny a ??cieo
eii?aeeiaoe?eieo aoceao.

3. Aea/aii oa?aeoa? aca?iiae?? Acio- oa Eenaiueai?nieo i?aai?/ieo niieoe
c oe?ai?aeieie eeneioaie. Iieacaii, ui oey aca?iiae?y ia i?eaiaeeoue aei
?oeioaaiiy eiiieaeniiai ai?iio, a i?e?aeiaiiy N-, O-ai?nieo niieoe
a?aeaoaa?oueny c ooai?aiiyi eiiieaenieo eao?ii?a. Anoaiiaeaii aieea
i?e?iaee, aoaeiae oa iniiaiino? ciai?oiueinoa?ieo i?aai?/ieo eao?ii?a oa
i?e?iaee Iaoae?a-eiiieaeniooai?thaa/?a ia oa?aeoa? eieeaaeueieo niaeo??a
eiiieaen?a.

4. Aea/aia e?enoae?/ia aoaeiaa (i?iaaaeaii iiaiee ?aioaaiino?oeoo?iee
aiae?c) o?ueio oeiiaeo i?aaenoaaiee?a oe?ai?aeieo eiiieaen?a.
Anoaiiaeaii, ui aoiie Aiaeith a eao?iiao oeio ae?aioei??eeiaoai?th
?icoaoiaai? aneiao?e/ii i?ae aeaiia Eeniaaeie aoiiaie ea?aii?eueieo
a?oi, a aeey ai?ii?a [Mo(CN)8]4- — iaeii/anio iayai?noue a no?oeoo??
aeaio eii?aeeiaoe?eieo iiiaia?aiiee?a — aeiaeaeaaae?a oa aioei?ecie.

5. Anoaiiaeaii, ui oa?i?/ia no?ee?noue eiiieaen?a caeaaeeoue a?ae
i?e?iaee ciai?oiueinoa?ieo i?aai?/ieo eao?ii?a ?
Iaoae?a-eiiieaeniooai?thaa/?a. Cai?iiiiiaaii noaie oa?i?/iiai ?iceeaaeo
eiiieaen?a oa iieacaii, ui ?iceeaae eiiieaen?a ye c Acioai?nieie, oae ?
Eenaiueai?nieie eao?iiaie i?ioiaeeoue ca ni?eueieie noaiaie:

· aeaa?ae?aoaoe?y eiiieaen?a;

· a?aeuaieaiiy oa i??ie?c i?aai?/iiai eao?iio;

· ?iceeaae oe?ai?aeieo eeneio c ooai?aiiyi i?inoeo oe?ai?ae?a (aeey
eiiieaen?a Iie?aaeaio (IV), Oa?oio (???), Eiaaeueoo (???) aeiaeaoeiai
niinoa??aa?oueny a?aeiiaeaiiy ?o aei ieae/eo nooiai?a ieeniaiiy);

· ?iceeaae i?inoeo oe?ai?ae?a c aeae?eaiiyi acioo oa ooai?aiiyi
ea?a?ae?a iaoae?a, iaoae?a ? aoaeaoeth.

6. Anoaiiaeaii, ui aia?a?y aeoeaaoe?? oa cia/aiiy ia?aaeaeniiiaioe?eiiai
iiiaeieea aeey aoaio oa?i?/iiai ?iceeaaeo Acioai?nieo i?aai?/ieo
eao?ii?a oe?ai?aeieo eiiieaen?a ia?ao?aeieo iaoae?a caeaaeaoue a?ae
i?e?iaee ciai?oiueinoa?ieo eao?ii?a ? i?e?iaee
Iaoae?a-eiiieaeniooai?thaa/?a ? aeeaaeathoueny a iaae? eiiiainaoe?eiiai
aoaeoo. ?yaee e?iaoe/ii? no?eeino?, neeaaeai? a ii?yaeeo ciaioaiiy
aia?a?? aeoeaaoe??, ia ni?aiaaeathoue c ?yaeaie oa?i?/ii? no?eeino?
eiiieaen?a.

7. Anoaiiaeaii, ui a iaaiaeiiio na?aaeiaeu? iiaeia iaea?aeoaaoe ye
i?ino?, oae ? eiiieaeni? oe?ai?aee, neioac yeeo iaiiaeeeaee aai
oneeaaeiaiee o aiaeieo ?ic/eiao. Iieacaii, ui iaaiaeia na?aaeiaeua
aieeaa? ia ?aaeoe?eio caeaoi?noue, aeanoeaino? oa oioio?i?/io iiaaae?ieo
oe?ai?aeieo eiiieaen?a.

8. Aea/aii ?ia?aoth/? aeanoeaino? neioaciaaieo oe?ai?aeieo eiiieaen?a
ia?ao?aeieo iaoae?a a na?aaeiaeu? 3%-iiai ?ic/eio oei?eaeo iao??th, a
i?enooiino? aoeeaeioiaieo ? noeueoao?aaeoeoth/eo aaeoa??e oa a
eaeioa?aiaeo iaoa??aeao. Anoaiiaeaii, ui eiiieaene aaenaoe?aiioa?ao (??)
i-ai?iioaiie?th, aaenaoe?aiioa?ao (??) 2-ai?iii??eaeei?th,
ieoaoe?aiiiie?aaeao (IV) aaeneeae?aioei??eeiaoai?th oa
i?o?iciiaioaoe?aiioa?aoe (??) i?ii?e- ? aaeneeae?aioei??eeiaoai?th
iathoue aenie? caoeni? aeanoeaino? ? iiaeooue aooe aeei?enoai? aeey
caoenoo na?aaeiueiaoaeaoeaaeo noaeae o aiae? iai?ioieo oeeee?a, o
ii?nuee?e aiae? oa eaeioa?aiaeo iaoa??aeao.

Iniiaiee ci?no ?iaioe aeeeaaeaii o ioae?eaoe?yo:

1. Naiaieoei Ae.?. Neioac oa ?* niaeo?ineii?/ia aeine?aeaeaiiy
i?aaiiai?nieo aaenaoe?aii?ooaiao?a (II) // Oe?. o?i. aeo?i.- 1997.-O.
63, ?11.- N.10-13.

2. Naiaieoei Ae.?. Caeiiii??iino? oa?iie?co i?aaiiai?nieo oe?ai?aeieo
eiiieaen?a cae?ca (II), ?ooai?th (II), iie?aaeaio(IV) //
Oe?.o?i.aeo?i.-1997.-O.63, ?8.- N.80-85.

3. Naiaieoei Ae.?. Neioac oe?ai?aeieo eiiieaen?a a na?aaeiaeu?
ai?ioiiieo ?ic/eiiee?a // Oe?. o?i. aeo?i.- 1998. -O.64, ?5.- N.8-9.

4. Naiaieoei Ae.?. Aieea na?aaeiaeua ai?ioiiieo ?ic/eiiee?a ia
aeanoeaino? ai?iiieo oe?ai?aeieo eiiieaen?a // Oe?. o?i. aeo?i.- 1998.-
O.64, ?6.- N.85-88.

5. Naiaieoei Ae.?. Aeine?aeaeaiiy ?ia?aoth/eo aeanoeainoae i?aaiiai?nieo
oe?ai?aeieo eiiieaen?a aeayeeo ia?ao?aeieo iaoae?a // O?c.-o?i. iao.
iaoa??ae?a.- 1997.- O.3.- N.122. (Protective properties of organic
cyanide complexes of transition metals // Materials scienne.- 1997.-
V.33, N3.- P.388-389).

6. Naiaieoei Ae.?. E?iaoe/i? ia?aiao?e i?ioean?a oa?iie?co i?aaiiai?nieo
oe?ai?aeieo eiiieaen?a cae?ca (II), ?ooai?th (II), iie?aaeaio (IV) //
A?niee AeO “Euea?anueea iie?oaoi?ea”. Oai?y, oaoiieia?y ?a/iaei oa ?o
canoinoaaiiy.-Euea?a, 1997.- ?316.- N.56-59.

7. Naiaieoei Ae.?. Oa?i?/iee ?iceeaae i?aaiiai?nieo aaenaoe?aii?ooaiao?a
// A?niee “Euea?anueea iie?oaoi?ea”. Oai?y, oaoiieia?y ?a/iaei oa ?o
canoinoaaiiy.- Euea?a, 1997.- ?316.- N.59-62.

8. Naiaieoei Ae.E., Ai?iaay I.ss. Enneaaeiaaiea aaenaoeeaiioa??aoia (II)
aooee-, aeeyoee- e o?eyoeeaiiiiey // Eii?ae. oeiey.- 1985.- O.11, aui.
12.- N.1670-1672.

9. Naiaieoei Ae.E., Ai?iaay I.ss., TH?/ae A.A. Oeceei-oeie/aneia
enneaaeiaaiea aaenaoeeaiioa??aoia (II) aieeeiey, aaiceaeeiey e
aaicio?eaciea // Eii?ae. oeiey.- 1986.- O.12, aui. 4.- N.502-504.

10. Naiaieoei Ae.E., Ai?iaay I.ss., sso/eoei E.E. Eiiieaenu
aeaeacenoineia?iaeenoie eeneiou n yoeeaiaeeaieiii e aeeyoeeaio?eaieiii
// Eii?ae. oeiey.- 1987.- O.13, aui. 12.- N.1639-1641.

11. Ai?iaay I.ss., Oacaae C.A., Naiaieoei Ae.E. Enneaaeiaaiea
aaenaoeeaiioa?aoia aaiceeaieiey, i-oieoeaeeiey e i-aieceaeeiey // AE.
iai?aai. oeiee.- 1990.- O.35, aui. 2.- N.382-385.

12. Ieoaeaae/ E.I., Eoioue I.E., Naiaieoei Ae.E. Neioac e
oeceei-oeie/aneia enneaaeiaaiea «iieaauo» nieae oeeaieaeiuo eeneio
aeaeaca (II, III) e eiaaeueoa (III) n aeeaioeie?eeiaoaiii // Eii?ae.
oeiey.- 1978.- O.4, aui. 11.- N.1695-1698.

13. Eoioue I.E., Ieoaeaae/ E.I., Naiaieoei Ae.E. I oeeaiieiiieaenao
ia?aaioea (II), eiaaeueoa (II), ieeaey (II) n aeeiaoeenoeueoieneaeii,
aeeiaoeeoi?iaieaeii, aeeiaoeeaoeaoaieaeii // Eii?ae. oeiey.- 1979.- O.5,
aui. 5.- N.685-688.

14. Eoioue I.E., Naiaieoei Ae.E., Aeceo E.I. Eii?aeeiaoeeiiiua
niaaeeiaiey oeeaieaea eiaaeueoa (II) n iiiiieenyie oinoeiia // Eii?ae.
oeiey.- 1980.- O.6, aui. 6.- N.914-917.

15. Eoioue I.E., Naiaieoei Ae.E., AEoeianeee A.ss. Iaioaoeeaiieiiieaenu
eiaaeueoa (III) n aeeiaoeenoeueoieneaeii e aeeiaoeeoi?iaieaeii //
Eii?ae. oeiey.- 1981.- O.7, aui. 10.- N.1489-1491.

16. Eoioue I.E., Naiaieoei Ae.E., Ieoaeaae/ E.I. Iieo/aiea aiiiieaauo
nieae oeeaiieiiieaenia Co (II), Ni (II), Pd (II) a iaaiaeiuo
?anoai?eoaeyo // Oe?. oei. aeo?i.- 1983.- O.49, ?3.- N.121-122.

17. Eoioue I.E., A?aoeaia I.A., Naiaieoei Ae.E. Oioieec
ieoaoeeaiiiieeaaeaiiaie eeneiou a aeeiaoeenoeueoieneaea //
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18. Niaeo?ineiie/aneia e ?aioaaiia?aoe/aneia enneaaeiaaiea
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neeaae eiiieaen?a ? niin?a eii?aeeiaoe?? e?aaiae?a. Ioe?iaii aieea
i?e?iaee Acio- ? Eenaiueai?nieo i?aai?/ieo eao?ii?a, e?aaiae?a,
Iaoae?a-eiiieaeniooai?thaa/?a ia aoaeiao oe?ai?aeieo eiiieaen?a.
Aeine?aeaeaii e?enoae?/io no?oeoo?o o?ueio oeiiaeo i?aaenoaaiee?a
oe?ai?aeieo eiiieaen?a. Anoaiiaeaii i?e?iaeo ca’yceo i?aai?/iiai eao?iio
c eiiieaeniei oe?ai?aeiei ai?iiii. Aecia/aia iine?aeiai?noue
o?ceei-o?i?/ieo i?ioean?a, ye? i?io?eathoue i?e oa?i?/iiio ?iceeaae?
oe?ai?aeieo eiiieaen?a. Noi?ioeueiaaii iniiai? caeiiii??iino? ?o
oa?iie?co. Anoaiiaeaii ei?aeyoe?th i?ae i?e?iaeith ciai?oiueinoa?ieo
ii??aeo eao?ii?a, Iaoae?a-eiiieaeniooai?thaa/?a oa oa?i?/iith ?
e?iaoe/iith no?ee?noth eiiieaen?a. Anoaiiaeaii, ui ?yaee oa?i?/ii?
no?eeino? oe?ai?aeieo eiiieaen?a ia ni?aiaaeathoue c ?yaeaie ?o
e?iaoe/ii? no?eeino?. Anoaiiaeaii, ui aaee/eie aia?a?? aeoeaaoe?? oa
ia?aaeaeniiiaioe?eiiai iiiaeieea caeaaeaoue a?ae i?e?iaee ii??aeo
eao?ii?a, Iaoae?a-eiiieaeniooai?thaa/?a oa aeeaaeathoueny a iaae?
eiiiainaoe?eiiai aoaeoo. Iieacaii iiaeeea?noue i?aeoe/iiai aeei?enoaiiy
oe?ai?aeieo eiiieaen?a aeey aioeei?ic?eiiai caoenoo noae? a nenoaiao
iai?ioiiai aiaeiiinoa/aiiy, a ii?nuee?e aiae?, a i?enooiino?
aoeeaeioiaieo oa noeueoao?aaeoeoth/eo aaeoa??e oa a eaeioa?aiaeo
iaoa??aeao.

Eeth/ia? neiaa: oe?ai?aei? eiiieaene, d-Iaoaee, N-, O-ai?ni? i?aai?/i?
niieoee, neioac, ?*-niaeo?e, oa?iie?c, ?ia?a?oi?e ei?ic??.

Naiaieoei Ae.E. Oeeaieaeiua eiiieaenu ia?aoiaeiuo iaoaeeia n Acio- e
Eenei?iaeniaea?aeaueie niaaeeiaieyie. ?oeiienue.

Aeenna?oaoeey ia nieneaiea o/aiie noaiaie aeieoi?a oeie/aneeo iaoe ii
niaoeeaeueiinoe 02.00.01- iai?aaie/aneay oeiey.- Eueaianeee
ainoaea?noaaiiue oieaa?neoao eiaie Eaaia O?aiei, Eueaia, 1999.

Aeenna?oaoeey iinayuaia enneaaeiaaieth oeeaieaeiuo eiiieaenia
ia?aoiaeiuo iaoaeeia n Acio- e Eenei?iaeniaea?aeaueie niaaeeiaieyie a
ea/anoaa eaoeiiia eee eeaaiaeia. Neioace?iaaiu e enneaaeiaaiu /aou?a
a?oiiu iiauo oeeaieaeiuo eiiieaenia (AH)nH4-n[M(CN)m], aaea A — aiieae e
N-niaea?aeauea i?aaie/aneea niaaeeiaiey, M= Fe2+, Ru2+, n=1-4, m=6; M=
Mo4+, n=1-4, m=8; (DH)xHn-x[M(CN)m], aaea D — aeeaioeie?eeiaoai e aai
i?iecaiaeiua, M= Fe2+, Fe3+, Co3+, Mo4+ n=2-4, x=2-4, m=6,8 e M(CN)2L,
aaea M=Mn2+, Co2+, Ni2+, L=aeeiaoeenoeueoieneae, aeeiaoeeoi?iaieae,
aeeiaoeeaoeaoaieae, oinoeiieneaeu, a oaeaea (NH4)2[Co(CN)5L] (L=DMSO,
DMFA), (NH4)6[Co2(CN)10].3DMFA, (NH4)2[Pd(CN)4].3DMSO, (NH4)2[Ni(CN)4],
Ag3[Mo(CN)7DMSO]. Onoaiiaeai ninoaa eiiieaenia e niinia eii?aeeiaoeee
eeaaiaeia. Ioeaiaii aeeyiea i?e?iaeu Acio- e Eenei?iaeniaea?aeaueo
i?aaie/aneeo eaoeiiia, eeaaiaeia, Iaoaeeia-eiiieaeniia?aciaaoaeae, ia
no?iaiea oeeaieaeiuo eiiieaenia. Onoaiiaeaii, /oi ia iieiaeaiea /anoiou
aaeaioiuo eieaaaiee a?oiiu Nwmetafile8? ??‰????????????
???????????yyy????.????1?????? ???????
@????&??yyyy?????Ayyy0???@??p?? ???&?
?MathType??????u@th??????(DH)xHn-x[M(CN)m] aeeyao i?e?iaea, ?acia?
aiaoianoa?iuo iieaauo eaoeiiia, iaee/ea caianoeoaeae e aeiiieieoaeueiuo
i?ioiiiaeoeaioi?iuo oeaio?ia a i?aaie/aneeo iniiaaieyo, a oaeaea,
i?e?iaea Iaoaeeia-eiiieaeniia?aciaaoaeae. Onoaiiaeaii, /oi i?e
acaeiiaeaenoaee N-, O-niaea?aeaueo niaaeeiaiee n oeeaieaeiuie eeneioaie
i?ienoiaeeo ia?aciaaiea eiiieaeniuo eaoeiiia, a ?ac?ooaiea eiiieaeniuo
aieiiia ia iaaethaeaaony. Iieacaii, /oi a niaoaii-eeaaiaeiuo eiiieaenao
eii?aeeiaoeey eeaaiaeia i?ienoiaeeo /a?ac aoiiu eenei?iaea a aeaea
iaeo?aeueiuo iieaeoe. Eiiieaenu oeia M(CN)2L nio?aiytho iieeia?ioth
no?oeoo?o e eii?aeeiaoeey eeaaiaeia i?ienoiaeeo aneaaenoaee
iayeaeaaeaioiinoe aoiiia iaoaeeia, iaoiaeyueony a ?acee/iuo
eii?aeeiaoeeiiiuo oceao.

Enneaaeiaaii e?enoaeee/aneoth no?oeoo?o o?ao oeie/iuo i?aaenoaaeoaeae
oeeaieaeiuo eiiieaenia (DH)2[Fe(CN)5NO], (NH4)4[Mo(CN)8].0.5H2O,
(NH4)4[Ru(CN)6]. Iieacaii, /oi i?e ia?aciaaiee aeeaioeie?eeiaoaieaaiai
eaoeiia i?ioii I+ i?eniaaeeiyaony e iaeiiio ec ea?aiieeueiuo aoiiia
eenei?iaea iieaeoeu aeeaioeie?eeiaoaia, a n ninaaeiei aoiiii eenei?iaea
ia?acoao e?aieoth aiaei?iaeiith naycue. Onoaiiaeai oa?aeoa? nayce
i?aaie/aneiai eaoeiia n eiiieaeniui oeeaieaeiui aieiiii. Aeey aieiiia
[Mo(CN)8]4- aia?aua onoaiiaeaii iaeiia?aiaiiia iaee/ea a no?oeoo?a aeaoo
eii?aeeiaoeeiiiuo iieeyae?ia — aeiaeaeayae?a e aioei?eciu.

Ii?aaeaeaia iineaaeiaaoaeueiinoue oeceei-oeie/aneeo i?ioeannia, eioi?ua
i?ioaeatho i?e oa?ie/aneii ?aceiaeaiee eiiieaenia. I?aaeeiaeaiu noaiu
oa?ie/aneiai ?aniaaea eiiieaenia e onoaiiaeaii, /oi ?aceiaeaiea
eiiieaenia eae n Acioniaea?aeaueie, oae e n Eenei?iaeniaea?aeaueie
iieaauie eaoeiiaie i?ioaeaao /a?ac ?yae iaueo noaaeee: aeeaeae?aoaoeey
eiiieaenia; iouaieaiea e ie?ieec i?aaie/aneeo eaoeiiia; ?aceiaeaiea
oeeaieaeiuo eeneio (aeey eiiieaenia Mo(IV), Fe(III), Co(III)
aeiiieieoaeueii iaaethaeaaony ainoaiiaeaiea eo aei Mo(II), Fe(II),
Co(II)); ?aceiaeaiea i?inouo oeeaieaeia aei ea?aeaeia iaoaeeia eee
iaoaeeia e oaea?iaea. Ca oaiia?aoo?aie ia/aea i?ioeana oa?iieeca
oeeaieaeiua eiiieaenu Fe(II), Ru(II), Mo(IV) n iieaauie eaoeiiaie
aeaeyony ia aeaa a?oiiu:

· eiiieaenu n tia/.=150-190iN, eioi?ua niaea?aeao a iieaaii eaoeiia
i?aaie/aneea aieiu n ?Eb<5; · eiiieaenu n tia/.=100-170iN, eioi?ua niaea?aeao a iieaaii eaoeiia i?aaie/aneea aieiu n ?Eb>7.

Oaiia?aoo?a ia/aea oa?iieeca caaeneo io i?e?iaeu e iniiaiinoe aieiia,
aoiaeyueo a iieaaua eaoeiiu, iaee/ey a ieo caianoeoeeae e
aeiiieieoaeueiuo i?ioiiiaeoeaioi?iuo a?oii, a oaeaea io i?e?iaeu
iaoaeeia-eiiieaeniia?aciaaoaeae.

Onoaiiaeaii ei??aeyoeeth iaaeaeo i?e?iaeie aiaoianoa?iuo iieaauo
eaoeiiia, Iaoaeeia-eiiieaeniia?aciaaoaeae e oa?ie/aneie e eeiaoe/aneie
onoie/eainoueth oeeaieaeiuo eiiieaenia. Ii?aaeaeaii, /oi ?yaeu
oa?ie/aneie onoie/eainoe oeeaieaeiuo eiiieaenia n Acioniaea?aeaueie
iieaauie eaoeiiaie ia niaiaaeatho n ?yaeaie eo eeiaoe/aneie
onoie/eainoe. Onoaiieaii, /oi aaee/eiu yia?aee aeoeaaoeee e
i?aaeyeniiiaioeeaeueiiai iiiaeeoaey caaenyo io i?e?iaeu iieaauo
eaoeiiia, Iaoaeeia-eiiieaeniia?aciaaoaeae e oeeaaeuaathony a ?aiee
eiiiainaoeeiiiiai yooaeoa.

Iieacaii, /oi a n?aaea ai?ioiiiuo ?anoai?eoaeae (DMSO, DMFA, DMAA),
eniieuecoy oi?ioi ?anoai?eiue a ieo oeeaieae aiiiiey, iiaeii iieo/aoue
ianieueaaoe?iaaiiua e nieueaaoe?iaaiiua oeeaieaeu, auaeaeeoue aiiieeiua
niee oeeaieaeiuo eeneio .eioi?ua iaaiciiaeii iieo/eoue a aiaeiie n?aaea.
Aeaiioth iaoiaeeeo iiaeia ?aeiiaiaeiaaoue aeey neioaca iiauo oeeaieaeiuo
eiiieaenia. Onoaiiaeaii aeeyiea ai?ioiiiuo ?anoai?eoaeae ia
?aaeoeeiiioth niiniaiinoue e naienoaa oeeaieaeiuo eiiieaenia.

Iieacaia aiciiaeiinoue i?aeoe/aneiai eniieueciaaiey oeeaieaeiuo
eiiieaenia aeey aioeei??iceiiiie caueou noaee a nenoaiao iai?ioiiai
aiaeiniaaaeaiey, a ii?neie aiaea, a i?enoonoaee aoeeaeioiaiuo e
noeueoao?aaeooee?othueo aaeoa?ee, a oaeaea a eaeie?ani/iuo iaoa?eaeao.
Onoaiiaeaii, /oi iaeeo/oea eiaeae?othuea naienoaa eiatho:
aaenaoeeaiioa??aou (??) i-aieiioaiieey e 2-aieiiie?eaeeiey;
ieoaoeeaiiiieeaaeaou (IV) aeeyoeeaiiiiey e aaeneeaeeaioeie?eeiaoaiey;
ieo?iciiaioaoeeaiioa??aou (??) i?iiee- e aaeneeaeeaieie?eeiaoaiey.

Eeth/aaua neiaa: oeeaieaeiua eiiieaenu, d-Iaoaeeu, N-,O-niaea?aeauea
i?aaie/aneea niaaeeiaiey, neioac, EE-niaeo?u, oa?iieec, eiaeaeoi?u
ei??icee.

Semenyshyn D.I. Cyanide complexes of transition metals with Nitrogen-
and Oxygen- containing compounds.

The thesis for doctor’s degree by speciality 02.00.01 — inorganic
chemistry.- Ivan Franko Lviv State University, Lviv, 1999.

The thesis is devoted to the synthesis and physico-chemical
investigation of new cyanide complexes of transition metals with
Nitrogen- and Oxygen- containing compounds in external an internal
spheres. Composition of complexes and the way of ligand coordination has
been established. The influence of the nature of Nitrogen- and Oxygen-
containing organic cations, ligands, metal-complexings on cyanide
complexes structure has been evaluated. The crystal structure of three
typical cyanide complexes representatives has been investigated. The
nature of organic cation relation with complex cyanide anion has been
established. The succession of physico-chemical processes taking place
during thermal decomposition of cyanide complexes has been determined.
The general reregularities of their thermolysis have been formulated.
The correlation among the nature of external-sphere onium cations,
metal-complexings, thermal and kinetic stability of complexes has been
established. It has been ascertained that the raws of thermal stability
of cyanide complexes do not coicide with the raws of their kinetic
stability. It has been established that activation energy and
preexponential factor values depend on onium cations nature and
metal-complexings and are within the boundaries of compensation effect.
The possibility of practical application of cyanide complexes for
inhibitor protection of steel in reverce water-supply systems, in sea
water in the presents of acidophobic and sulphate reducing bacteria and
in lacquer paint matirials has been shown.

Key words: cyanide complexes, d-metals, N-, O-containing compounds,
synthesis, IR-spectra, thermolysis, corrosion inhibitors.

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