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Структурна хімія інтермедіатів купрокаталітичного перетворення ацетилену та його похідних: Автореф. дис… д-ра хім. наук / Б.М. Михалічко, Львів. нац

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32

Euea?anueeee iaoe?iiaeueiee oi?aa?neoao ?iai? ?aaia O?aiea

IEOAE?*EI AI?EN IE?IIIAE*

OAeE 548.736:546.561

NO?OEOO?IA O?I?ss ?IOA?IAAe?AO?A EOI?IEAOAE?OE*IIAI IA?AOAI?AIIss
AOeAOEEAIO OA EIAI IIO?AeIEO

02.00.01 — iai?aai?/ia o?i?y

Aaoi?aoa?ao

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

aeieoi?a o?i?/ieo iaoe

Euea?a — 1999

Aeena?oaoe??th ? ?oeiien.

?iaioa aeeiiaia ia eaoaae?? iai?aai?/ii? o?i?? Euea?anueeiai
iaoe?iiaeueiiai oi?aa?neoaoo ?iai? ?aaia O?aiea I?i?noa?noaa ina?oe
Oe?a?ie.

Iaoeiaee eiinoeueoaio

Io?oe?ei? iiiiaioe:

I?ia?aeia onoaiiaaaeieoi? o?i?/ieo iaoe, i?ioani?

Ienuee?a Ia?`yi A?eai?iae/, Euea?anueeee iaoe?iiaeueiee oi?aa?neoao
?iai? ?aaia O?aiea, i?ioani? eaoaae?e iai?aai?/ii? o?i??

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

Ai?ioeeia TH??e A?oae?eiae/, Oaeai?iaenueeee aea?aeaaiee oi?aa?neoao,
i?i?aeoi? c iaa/aeueii? ?iaioe

aeieoi? o?i?/ieo iaoe,

Aaeueiaieueaeo Aieiaeeie? Ieaaiae/,

O?ceei-o?i?/iee ?inoeooo caoenoo iaaeieeoiueiai na?aaeiaeua ? ethaeeie,

i. Iaeana, caa?aeoaa/ a?aeae?eii

aeieoi? o?i?/ieo iaoe,

Eaiiaea ?inoeneaa Aeieo?iae/,

Ee?anueeee iaoe?iiaeueiee oi?aa?neoao

?iai? Oa?ana Oaa/aiea, i?ioani? eaoaae?e iai?aai?/ii? o?i??

?inoeooo caaaeueii? oa iai?aai?/ii? o?i?? ?iai? A. ?. Aa?iaaenueeiai
IAI Oe?a?ie, i. Ee?aCaoeno a?aeaoaeaoueny: 16 aa?aciy 2000  ?. i 14
aiaeei? ia can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae 35.051.10 c
o?i?/ieo iaoe o Euea?anueeiio iaoe?iiaeueiiio oi?aa?neoao? ?iai? ?aaia
O?aiea I?i?noa?noaa ina?oe Oe?a?ie ca aae?anith: 79005, i. Euea?a, aoe.
Ee?eea ? Iaoiae?y, 6, o?i?/iee oaeoeueoao, aoae. ? 2.

C aeena?oaoe??th iiaeia iciaeiieoenue o a?ae?ioaoe? Euea?anueeiai
iaoe?iiaeueiiai oi?aa?neoaoo ?iai? ?aaia O?aiea (aoe. Ae?aaiiaiiaa, 5).

Aaoi?aoa?ao ?ic?neaiee 1 ethoiai 2000 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee
ss?aiei C. I.CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. Iiaeeea?noue canoinoaaiiy niieoe eoi?oio(I) a
?aaeoe?yo c o/anoth aoeaoeeaio ?aaeueii iiyaeeany iacaaeiaai aei
1900 ?., eiee noaea a?aeiiith aca?iiae?y i?ae CuCl ? C2H2, i?ioa
i?iieneiaiai iioe?aiiy aiie iaaoee a?aeoiae?, ye Iuetheaiae o
1929-31 ??. aia?oa cae?eniea eaoae?oe/io ie?aiia?ecaoe?th aoeaoeeaio o
eiioeaio?iaaiiio aiaeiiio ?ic/ei? CuCl ? NH4Cl ? iaea?aeaa
iiiia?i?eaoeaoeeai, yeee aeei?enoiao?oueny o ae?iaieoeoa? oei?ii?aiiaiai
eao/oeo. Caaaeyee nai?e aeinooiiino? aaeiaai?aee Cu(I) oaeaeei ciaeoee
canoinoaaiiy ye eaoae?caoi?e a ?aaeoe?yo c o/anoth aoeaoeeaio, oni?oii
eiieo?oth/e c oiene/ieie nieyie Hg(II) oa cia/ii aei?iae/eie niieoeaie
Pt(II) ? Pd(II), ui o?aaeeoe?eii aeei?enoiaoaaeenue a i?aai?/iiio
neioac?. Aeineoue neacaoe, ui nueiaiaei? aeecueei 40 i?ioean?a c o/anoth
aoeaoeeaiiaeo niieoe eaoae?cothoueny NuNl aai CuBr, /aoaa?oa /anoeia c
ieo ia? i?iieneiaa cia/aiiy.

Ia?o? oni?oi? ?iaioe Iuetheaiaea uiaei eoi?ieaoae?oe/iiai niiniao
iaea?aeaiiy iiiia?i?eaoeaoeeaio, aeaee iiooiao aaaaoueii aeine?aeieeai,
ye? c iaoith oaeineiiaeaiiy i?ioeano i?aaioee anoaiiaeoe eiai iaoai?ci.
Aeey ?icoi?iiy inoaiiueiai iaiao?aeii iaoe aeieeaaeio ?ioi?iaoe?th i?i
i?ii?aei? niieoee, ui ooai?ththoueny i?ae /an ia?aa?ao ?aaeoe??,
cie?aia, -, ,- ? -eiiieaene CuCl c aoeaoeeaiii oa eiai iio?aeieie, a?ae
o?i?/iiai neeaaeo oa aoaeiae yeeo caeaaeeoue aeo?ae ? iaa?oue oei
e?ioeaaiai i?iaeoeoo. Iaeiae iaoai?ci oe??? aaaeeeai? a i?iieneiaiio
a?aeiioaii? ?aaeoe?? ua aein? aei e?ioey ia c`yniaaiee, ui, a?aoo?, e
iiynith? ?ica?aeiino? a eiai o?aeooaaii?. Iaei??th c iniiaieo i?e/ei
oaeiai noaio aei iaaeaaiueiai /ano aoea a?aenooi?noue aeinoia??ii?
?ioi?iaoe?? i?i e?enoae?/io no?oeoo?o ?ioa?iaae?ao?a oeueiai i?ioeano:
ia?o? no?oeoo?i? aeine?aeaeaiiy i?ii?aeieo -eiiieaen?a CuCl c
aoeaoeeaiii oa eiai iio?aeieie c`yaeeeny ia ii/aoeo 90-o ?ie?a, iaeiae
aiie ia aoee nenoaiaoe/ieie. Aeey onoiaiiy i?ioe??/ o iiyniaiiyo
iaoai?cio ia?aa?ao ?aaeoe?? Iuetheaiaea, aaoi?ii ?icii/aoi (1992 ?.)
nenoaiaoe/ia aeine?aeaeaiiy aoaeiae ?ioa?iaae?ao?a eoi?ieaoae?oe/iiai
ia?aoai?aiiy aoeaoeeaio oa eiai iio?aeieo.

Na?aae iaoiae?a aea/aiiy aoaeiae ?a/iaeie a e?enoae?/iiio noai? aaeueie
?ioi?iaoeaiei ? ?aioaaiino?oeoo?iee aiae?c, c aeiiiiiaith yeiai iiaeia
aeyaeoe ?yae iniaeeainoae aoaeiae eii?aeeiaoe?eii? noa?e oeaio?aeueiiai
aoiia, aecia/eoe aaiiao?e/i? ia?aiao?e eii?aeeiiaaii? ia iaoae?/iiio
oeaio?? iieaeoee e?aaiaeo, ioe?ieoe aoaeoeai?noue oa ooi/ieoe i?e?iaeo
iaoae-e?aaiaeii? aca?iiae??. Ciaiiy oeeo ia?aiao??a iaiao?aeia ye aeey
iiyniaiiy ?aaeoe?eii? caeaoiino? i?ii?aeieo eiiieaen?a, oae ? aeoeaiino?
eaoae?caoi??a.

Iaeiae iaea?aeaiiy i?eaeaoieo aeey ?aioaaiino?oeoo?iiai aiae?co
e?enoae?a (aeey oeueiai iio??ai? ye?ni? iiiie?enoaee iaaaeeeeo ?ici???a
— 0.30.8 ii), noaei nai???aeiei “eaiaiai niioeeaiiy” ia oeyoo ae??oaiiy
cacia/aii? aeua i?iaeaie. Ine?eueee oaeiai oeio niieoee
oa?aeoa?ecothoueny iaaaeeeith no?ee?noth, ?o iaiao?aeii neioacoaaoe
a?ae?aco o aeaeyae? ie?aieo e?enoae?a, oieeath/e noaae?e
ia?ae?enoae?caoe??. A?aeii? iaoiaee neioaco oeueiai oeio niieoe
iaeii?eaeaoi?, ine?eueee eiiieaene ooai?ththoueny caeaa?eueoiai o
aeaeyae? ii?ioe?a oa e?enoae?/ieo c?inoe?a. Oiio iaiao?aeii aoei oaeiae
?ic?iaeoe iaoiaee iaea?aeaiiy i?eaeaoieo aeey ?aioaaiino?oeoo?iiai
aiae?co e?enoae?a.

Ca`ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie. ?iaioa aeeiiaia
o a?aeiia?aeiino? c iaoeiai-oaoi?/iith i?ia?aiith I?i?noa?noaa ina?oe
“14. Iiiiia?e, iiaa?oiaai-aeoeai? ?a/iaeie, iaiiaithaa/?, iiaeeo?eaoi?e
? ia?niaeoeai? oaoiieia?? iaea?aeaiiy iie?ia?ieo eiiiiceoieo iaoa??ae?a
ia ?o iniia?”, caoaa?aeaeaiith iaoeiai-ania?oiith ?aaeith ca oaoiaei
iai?yiii “O?i?y, o?i?/ia oaoiieia?y, o?i?/ia iaoeiiaoaeoaaiiy”, ii oai?
“No?oeoo?ia o?i?y eoi?ieaoae?oe/iiai i?ioeano iaea?aeaiiy
a?i?eaoeaoeeaio” (? aea?ae?a?no?aoe?? 0195V026233).

Iaoa oa caaea/? aeine?aeaeaiiy. Aea/eoe no?oeoo?iee aniaeo
eoi?ieaoae?oe/iiai ia?aoai?aiiy N2I2 oa eiai aiaeia?a, nie?ath/enue ia
?acoeueoaoe ?aioaaiino?oeoo?iiai aiae?co iaea?aeaieo e?enoae?/ieo
?ioa?iaae?ao?a, ui ooai?ththoueny ia ??cieo noaae?yo i?ioeano.

Aeey aeinyaiaiiy oe??? iaoe iaiao?aeii aoei:

?ic?iaeoe iaoiae neioaco i?eaeaoieo aeey ?aioaaiino?oeoo?iiai aiae?co
e?enoae?a;neioacoaaoe ?ioa?iaae?aoe eoi?ieaoae?oe/iiiai ia?aoai?aiiy
N2I2 oa eiai iio?aeieo o aeaeyae? ye?nieo iiiie?enoae?a;i?iaanoe
?aioaaiino?oeoo?iee aiae?c neioaciaaieo eiiieaen?a. Iaoeiaa iiaecia
iaea?aeaieo ?acoeueoao?a.

C aeiiiiiaith ?ic?iaeaiiai iaoiaeo ci?iiino?oiiiai aeaeo?io?i?/iiai
neioaco, a oaeiae iaoiaeii aaciina?aaeiuei? aca?iiae?? eiiiiiaio?a c
eaoae?oe/ieo neoai IO–NuCl–H2O–L (M — eao?iie eoaeieo iaoae?a, aiii?th ?
?ioeo i?aai?/ieo ai?i?a; O = Nl, Br, CN; L — NN-ai?nia i?aai?/ia
niieoea) aia?oa aoee aeae?eai? o aeaeyae? iiiie?enoae?a ? no?oeoo?ii
aea/ai? ?ioa?iaae?aoe eoi?ieaoae?oe/iiai ia?aoai?aiiy N2I2 oa eiai
iio?aeieo (35 niieoe); cia/ia ?o /anoeia, 15 niieoe, iaeaaeeoue aei
eeano aoeaoeeai?aeieo eoi?ioei?eaeieo (eoi?ioe?ai?aeieo) eiiieaen?a,
aeiaeiee i?aaenoaaiee yeeo ?ai?oa ?aioaaiino?oeoo?ii ia aea/aany.Ca?aae
iaea?aeaieo eoi?iaaeiaai?aeieo eiiieaen?a eoi?oio(?) aia?oa aeyaeaii
niieoee oeio guest-host oeaie?oii? aoaeiae.?aioaaiino?oeoo?ii
aeiaaaeaii, ui eaoae?oe/ia aeoeai?noue eiiieaen?a eoi?oio(I) coiiaeaia
caeaoi?noth a?oi NN cai?uoaaoe aoiie Cl a aeo?aeieo niieoeao.Iieacaii,
ui aeniea aoaeoeai?noue aca?iiae?? Cu(I)–(CC) a ,-eiiieaenao
aoeaoeeai?aeiiai oeio aeeeeeaia neia?a?ciii – (Nu(I)–CCR) oa –
(Cu(I)–(CC)) oei?a ca`ycoaaiiy.Aia?oa aeyaeaii, ui eiiieaeni? niieoee
Nu(?) oeio I(n-m)[CumXn] (X=Cl, CN) i?iyaeythoue caeaoi?noue aei
ethi?ianoeaioe??. I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a.

No?oeoo?ia ?ioi?iaoe?y i?i oi/iee neeaae oa aoaeiao ?ioa?iaae?ao?a
eoi?ieaoae?oe/ieo ?aaeoe?e c o/anoth aoeaoeeaiiaeo niieoe, iaiao?aeia
aeey ooi/iaiiy iaoai?cio i?iieneiai aaaeeeaiai i?ioeano
eoi?ieaoae?oe/ii? ie?aiia?ecaoe?? aoeaoeeaio oa eiai
iio?aeieo.?ic?iaeaiee iaoiae ci?iiino?oiiiai aeaeo?io?i?/iiai neioaco
i?eaeaoieo aeey ?aioaaiino?oeoo?iiai aiae?co e?enoae?a -eiiieaen?a
aaeiaai?ae?a eoi?oio(?), yeee caoeuaiee aeaiia iaoaioaie, iiaea aooe
aeei?enoaiee i?e aea/aii? ?ioeo i?ioean?a eoi?ieaoae?oe/ieo ?aaeoe?e
iaiane/aieo i?aai?/ieo niieoe.Caoeuaiee iaoaioii aeiao?ae, yeee
noino?oueny caeaoiino? aeayeeo eiiieaenieo niieoe Cu(?) aei
ethi?ianoeaioe??, iiaea aooe aeei?enoaiee a ?aae?iaeaeo?ii?oe?,
i?eeaaeiaoaeoaaii?, iaaeeoeei?, oiui aeey aeaioiaeaiiy ethi?iioi??a c
/a?aiiei, caeaiei aai nei?i na?o?iiyi.Io?eiai? ?acoeueoaoe iiaeooue aooe
ei?enieie aeey o?i?e?a-iai?aai?e?a oa niaoe?ae?no?a, ui caeiathoueny
aea/aiiyi e?iaoeee ? eaoae?co ?aaeoe?e c o/anoth aee?i?a, a oaeiae
aeei?enoiaoaaoenue i?e aeeeaaeaii? a?aeiia?aeieo niaoeeo?n?a c o?i??
eii?aeeiaoe?eieo niieoe. Iniaenoee aianie caeiaoaa/a. Oi?ioethaaiiy
iaoeiaiai iai?yieo, iinoaiiaea caaea/?, aea?? ia`?eo?a aeine?aeaeaiiy,
neioac niieoe, iaea?aeaiiy iiiie?enoae?a, aeine?aeaeaiiy ?o
oioiiaoiaeii, ?icoeo?iaoaaiiy e?enoae?/ii? no?oeoo?e, aiae?c,
?ioa?i?aoaoe?y oa ocaaaeueiaiiy ?acoeueoao?a neeaaea? iniaenoee aianie
caeiaoaa/a. Ianeae aeeo?aeoe?eieo aeaieo ia iiiie?enoaeueieo
aeeo?aeoiiao?ao aoee io?eiai? ni?eueii c i?ioani?ii Ienuee?aei I. A.
(aeeo?aeoiiao? AeA?*-1) oa i?ioani?ii Aeiayeii O. (aeeo?aeoiiao? EI-4,
?inoeooo O?i?? A?ioeeaanueeiai oi?aa?neoaoo, Iieueua;), a aeai? ia
ii?ioeiaiio aeeo?aeoiiao?? (HZG-4) — ?acii c? no. iaoe. ni?a?.
Aeaaeaeiaei A. I. AI?-niaeo?ineii?/i? iii??e e?enoae?a iaei??? c niieoe
cae?enithaaeenue aeieoi?ii Eioeuea?i-A?ecae E. (Iaaeaaia?/iee
oi?aa?neoao *ainoioiae, Iieueua; niaeo?iiao? EPR — SE-X/25A/B). Ie?ai?
?aioaai?anuee? aeine?aeaeaiiy aoee i?iaaaeai? ni?eueii c e.o.i. Iaconii
I. Ae. (?anioae?ea Iieaeiaa), a oaeiae e.o.i. Aenaeue?oaeii E. A. ?
e.o.i. Ai??oi?eii ?. A.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iniiai? iieiaeaiiy oa ?acoeueoaoe
?iaioe aeeeaaeai? ia VI Ia?aae? c e?enoaeio?i?? iai?aai?/ieo ?
eii?aeeiaoe?eieo niieoe (Euea?a, 1992), XIV ?a?iiaenuee?e
e?enoaeia?ao?/i?e eiioa?aioe?? (Ainoaaea – I?aea?eaiaee, 1992), ???
Nan?? c i?iaeai i?eeeaaeii? e?enoaeio?i?? (Naieo-Iaoa?ao?a – ?in?y,
1993), XIV Oe?a?inuee?e eiioa?aioe?? c iai?aai?/ii? o?i?? (Ee?a, 1996),
VI Iaoeia?e eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy” (Euea?a, 1997),
? Iaoe?iiaeuei?e e?enoaeio?i?/i?e eiioa?aioe?? (*i?iiaieiaea – ?in?y,
1997) oa ia iaoeiaeo eiioa?aioe?yo Euea?anueeiai iaoe?iiaeueiiai
oi?aa?neoaoo ?iai? ?aaia O?aiea (Euea?a, 1996, 1997, 1998, 1999 ??.).

Ioae?eaoe??. Iaoa??aee aeena?oaoe?? i?aaenoaaeai? a 31 ioae?eaoe??, a
oiio /ene? a 23 noaooyo o iaoeiaeo oaoiaeo aeaeaiiyo ? 3 iaoaioao.

No?oeoo?a oa ia`?i aeena?oaoe??. Aeena?oaoe?eia ?iaioa neeaaea?oueny c?
anooio, naie ?icae?e?a c aeeeaaeii ?acoeueoao?a, aeniiae?a, nieneo
aeei?enoaieo aeaea?ae oa aeiaeaoe?a. Aeena?oaoe?y aeeeaaeaia ia 382
noi??ieao (aeeth/ath/e 49 noi?. aeiaeaoe?a), i?noeoue 63 oaaeeoei oa 97
?enoie?a. Nienie oeeoiaaii? e?oa?aoo?e iae?/o? 180 iaeiaioaaiue.

INIIAIEE CI?NO AeENA?OAOe??.

O anooi? ?ice?eaa?oueny aeooaeuei?noue oaiaoeee aeine?aeaeaiue,
aecia/a?oueny iaoa oa noaaeoueny caaaeaiiy ?iaioe, a?aeia?aaeaii iaoeiao
iiaecio oa i?aeoe/io oe?ii?noue iaea?aeaieo ?acoeueoao?a.

?icae?e 1. Aca?iiae?y aoeaoeeaio oa eiai iio?aeieo c nieyie eoi?oio(?).

Aeoiaey/e c e?oa?aoo?ieo aeaieo, ?icaeyaea?oueny aca?iiae?y NN-ai?nieo
i?aai?/ieo niieoe c nieyie Nu(I), ui ia? i?noea i?ae /an
eoi?ieaoae?oe/ieo ia?aoai?aiue N2I2 oa eiai iio?aeieo a eiioeaio?iaaieo
aiaeieo ?ic/eiao INl i CuCl.

Aca?iiae?y aoeaoeeaio oa eiai iio?aeieo c CuCl a eiioeaio?iaaieo
aiaeieo ?ic/eiao INl i?ae /an ia?aa?ao ?aaeoe?? Iuetheaiaea

[2NH4Cl, 3CuCl, H2O]eiioe.

2nHCCH nH2N=NI–CCH + nC2H2

?Iii/aoeiaa  4; t80o C

[2NH4Cl, 3CuCl, H2O]eiioe.

nH2N=NI–CC–CH=CH2 oa ?io? ie?aiia?e,

aai nii??aeiaii? ?aaeoe?? a?ae?ioe?aioaaiiy N2I2 (neioac ae?eeii?o?eeo)

[2NH4Cl, 3CuCl
(CuCN), H2O]eiioe.

nHCCH + nHCN nH2N=NI–CN,

?Iii/aoeiaa  4; t85o C

noi?iaiaeaeo?oueny ooai?aiiyi ??ciiiai?oieo ca i?e?iaeith, neeaaeii oa
aoaeiaith ?ioa?iaae?ao?a, ye? a no?oeoo?iiio a?aeiioaii? aeyaeeenue
i?aeoe/ii ia aea/aieie (?c 44 a?aeiieo a e?oa?aoo?? e?enoae?/ieo
?ioa?iaae?ao?a no?oeoo?ii aea/aieie aeyaeeinue eeoa 6 niieoe). Ii?yae c
oeei ?nio? /eiaei ?ia?o, a yeeo i?noyoueny a?aeiiino? i?i aoaeiao
??ciie?aaiaeieo -, ,- oa -eiiieaen?a c aoeaoeeaiii ? eiai iio?aeieie
(aoeeee?/ieie oa oeeee?/ieie) ia?aaaaeii c iaaaeiaai?aeieie nieyie
Cu(I). Oi/a oe? niieoee aaciina?aaeiuei ia ooai?ththoueny a eaoae?oe/ieo
?ic/eiao nenoaie Iuetheaiaea, iaeiae aeey aeyaeaiiy noa?aio?i?/ieo
caeiiii??iinoae aca?iiae?? Cu(I) — a?oia CC aiie ?icaeyaeathoueny a
?icae. 2.

?icae?e 2. E?enoae?/ia no?oeoo?a eoi?iaaeiaai?aeieo eiiieaen?a oa
eiiieaen?a eoi?oio(?) c NN-ai?nieie i?aai?/ieie e?aaiaeaie.

Ia ii/aoie 1998 ?ieo a e?oa?aoo?? aoee a?aeiino? i?i 91 no?oeoo?ii
aea/aiee eiiieaen Nu(I) c NN-ai?nieie i?aai?/ieie e?aaiaeaie, c ieo 41 —
eiiieaene c iaaaeiaai?aeieie nieyie Nu(I), 16 — eiiieaene ia iniia?
aoeaoeeai?ae?a Nu(I) ? 33 — niieoee c aaeiaai?aeaie eoi?oio(?) (iaeei
eiiieaen c NuCN). An? a?aeii? eiiieaene aaeiaai?ae?a eoi?oio(?) c
NN-ai?nieie e?aaiaeaie (33 niieoee) ? oeiiaeie -eiiieaenaie, ia?aaaaeia
a?eueo?noue c yeeo iaeaaeeoue oeeee?/iei (14 -eiiieaen?a) oa aoeeee?/iei
aeecai?uaiei iio?aeiei N2I2 (10 -eiiieaen?a). C inoaii?o 6 — -eiiieaene
c aeeai?iaie, a yeeo a?oia NN i?noeoueny ana?aaeei? iieaeoee. Iaeiaio
/eneaiiith a?oiith ? -eiiieaene NuCl c aoeaoeeaiii (5 niieoe) oa
iiiicai?uaieie iio?aeieie N2I2 (4 niieoee). Eiiieaene NuCl c aeeai?iaie,
ui i?noyoue oa?i?iaeueio NN-a?oio, ia iaee aeiaeiiai no?oeoo?ii
aea/aiiai i?aaenoaaieea.

Ioaea, i?ioeane eiiieaeniooai?aiiy a eaoae?oe/ieo nenoaiao
IO–CuCl–H2O–L (I — eao?iie eoaeieo iaoae?a, aiii?th oa i?ioiiiaai?
ai?ie; O=Nl, Br, CN; L — NN-ai?nia i?aai?/ia niieoea) aea/ai?
iaaeinoaoiuei.

Na?aae iienaieo a e?oa?aoo?? eoi?iaaeiaai?aeieo niieoe c aoeaoeeaiii oa
eiai iio?aeieie no?oeoo?i? a?aeiiino? ? eeoa i?i aeaye? -eiiieaene,
oiae? ye no?oeoo?a eoi?ioei?eaeieo eiiieaen?a aoeaoeeai?aeiiai oeio
acaaae? ia a?aeiia, oi/, ca?aeii e?iaoe/ieo aeaieo, naia ?o ooai?aiiyi
aecia/a?oueny eoi?ieaoae?oe/ia ia?aoai?aiiy N2I2.

Aaeaeaaoia i?aaenoaaeaiiy iaoai?cio ia?aa?ao eoi?ieaoae?oe/ii?
ie?aiia?ecaoe?? N2I2 oa nii??aeiaieo ?aaeoe?e iaiiaeeeaa aac ciaiiy
aoaeiae ?ioa?iaae?ao?a, ui aeieeathoue ia ??cieo noaae?yo i?ioeano.

?icae?e 3. Neioac oa ?aioaaiino?oeoo?ia aeine?aeaeaiiy e?enoae?/ieo
?ioa?iaae?ao?a eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio oa eiai
iio?aeieo.

O ?icae?e? iienaii iaoiaee iaea?aeaiiy ? neioaco i?eaeaoieo aeey
?aioaaiino?oeoo?iiai aiae?co iiiie?enoae?a eiiieaen?a, ui ooai?ththoueny
a i?ioean? eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio oa eiai iio?aeieo,
no?ee?noue oa aeaye? aeanoeaino? neioaciaaieo e?enoae?/ieo
?ioa?iaae?ao?a, iniaeeaino? ?aioaai?anueei? ceiiee e?enoae?a oa
?acoeueoaoe AI?-niaeo?ineii?/iiai aeine?aeaeaiiy e?enoae?a eiiieaeno
Rb11[Cu2I(H2O)2][CuI15Cl24(CuIICl6)].

?ic?iaeaii iaoiae ci?iiino?oiiiai aeaeo?io?i?/iiai neioaco e?enoae?a
eiiieaen?a, nooue yeiai iieyaa? o a?aeiiaeaii? c aeiiiiiaith ci?iiiai
no?oio NuX2 (X=Cl, Br) a i?enooiino? NN-ai?nii? niieoee (L) o
aiaeii-nie?oiaiio ?ic/ei? ia i?aeieo aeaeo?iaeao:

Nuo + NuX2 + L 2CuClL.

I?e oeueiio canoiniaothoueny aeaa ??cieo ae?aiaciie aaee/eie
i?eeeaaeaii? cciai? iai?oae ci?iiiai no?oio — 0.203 A ? 0.50.9 A.
Inoaii? /anoi ni?e/eith? ??no e?enoae?a eoi?iaaeiaai?aeieo -eiiieaen?a
??cieo iie?ii?oieo iiaeeo?eaoe?e oa noao?iiao???, ye? aeiiiiaaathoue
aaciina?aaeiuei io?eioaaoe aai iiaeaethaaoe ia iniia? aeecueei? aiaeia??
?ioa?iaae?aoe, ui aeieeathoue a ?ic/ei? i?ae /an ia?aa?ao
eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio oa eiai iio?aeieo.

Oeae iaoiae aeicaiey? iaa?oue iaea?aeoaaoe e?enoaee eiiieaen?a, ye?
?ioei niiniaii io?eiaoe i?aeoe/ii iaiiaeeeai. Oae, aeoiaey/e c
iiiia?i?eaoeaoeeaio (IAA) iaea?aeaoe e?enoaee eiai eoi?iaaeiaai?aeieo
eiiieaen?a iai ia aaeaeinue, ui iiynith?oueny cia/iith ?aaeoe?eiith
caeaoi?noth IAA, yeee a i?enooiino? NuCl a?ae?aco aai iie?ia?eco?oueny,
aai ae a?ae?ioei?o?oueny ii iio??eiiio ca`yceo. Oiio aeey aeine?aeaeaiue
ie ciooai? aoee, cai?noue IAA, a?aoe i?iia?a?eiaee nie?o (IN), iieaeoea
yeiai oaae i?noeoue oa?i?iaeueio aoei?eueio a?oio ? oiio iiaea neoaoaaoe
iaeaea aaeaeaaoiith iiaeaeeth iiaaae?iee oa?i?iaeueieo aoeaoeeai?a, ui
ooai?ththoueny i?ae /an ia?aa?ao ?aaeoe?? Iuetheaiaea. Iaeiae ca iaaieo
oiia NuCl caeaoai eaoae?coaaoe ?iciaae iieaeoee IN aei N2I2, yeee aeae?
iiaea aeeia?ecoaaoenue a IAA ca noaiith:

HCCCH2OH HCCCI=O

HCCCOOH + CuCl HCCH + CO2.

2HCCHHCCCH=CH2.

Ooai?aiee in situ IAA aeaa 2 e?enoae?/i? eoi?ioei?eaei? eiiieaene
[Cu25Cl17(CCCH=CH2)8]14H2O i [Cu7Cl7(HCCCH=CH2)3].

Ioaea, c aeiiiiiaith i?ea?iaeueiiai iaoiaeo ci?iiino?oiiiai
aeaeo?io?i?/iiai neioaco oa aaciina?aaeiueith aca?iiae??th eiiiiiaio?a
nenoaie Iuetheaiaea IX–CuCl–H2O–L (M – K+, Rb+, Cs+, NH4+, Him+
(?i?aeacie?e), Ipy+ (i??eaeei?e), Ian+ (ai?e?i?e), Imea+
(iiiiaoaiieaiii?e); X – Cl, Br, CN; L – HCCH, INNNI=NI2, INNNI2II,
NI2=NINI2NNNI2NI=NI2) aia?oa aoei aeae?eaii o aeaeyae? ye?nieo
iiiie?enoae?a ? ?aioaaiino?oeoo?ii aea/aii 35 niieoe – ?ioa?iaae?ao?a
(aai ?o aeecueeeo iiaeaeae) eoi?ieaoae?oe/iiai ia?aoai?aiiy N2I2 oa eiai
iio?aeieo, ui ooai?ththoueny ia ??cieo noaae?yo i?ioeano.

I?ii?aei? niieoee oa?aeoa?ecothoueny ii??aiyii iaaaeeeith no?ee?noth,
ui coiiaeth? ?o ?aaeoe?eio caeaoi?noue oa ni?ey? iiaeaeueoei
ia?aoai?aiiyi. Oey aeanoea?noue ?ioa?iaae?ao?a ua a?eueo i?eoaiaiia ?
aeey ?o e?enoae?/ii? oi?ie: ia iia?o?? (iniaeeai aieiaiio) e?enoaee
aaaaoueio neioaciaaieo eiiieaen?a ?iceeaaeathoueny ca aeineoue ei?ioeee
i?ii?aeie /ano ca ?aooiie ieeniaiiy Nu(I) oa ao?aoe e?aaiaeo.
Iaea?eueoith no?ee?noth oa?aeoa?ecothoueny niieoee c aoeaoeeai?aeiei
oeiii ca`yceo Nu–C, oiae? ye -eiiieaene (c? ca`yceaie Cu–(CC))
iaeinoaa?euei?; a?aeiinii a?eueoith no?ee?noth oa?aeoa?ecothoueny
e?enoaee ai?iiieo eoi?iaaeiaai?aeieo eiiieaen?a. Oea a?aoiaoaaeinue i?e
i?iaaaeaii? ?aioaaiino?oeoo?ieo aeine?aeaeaiue, yea i?iaiaeeee iaoiaeii
iiiie?enoaeo (aaoiaeeo?aeoiiao?, IiE-aei?ii?ithaaiiy, 2 560i, F  4 (F))
aai (a ie?aieo aeiaaeeao) ii?ioeiaith aeeo?aeoiiao???th
(aaoiaeeo?aeoiiao?, NuE-aei?ii?ithaaiiy, 2 8110i, e?ie neaioaaiiy
0.02i); an? aac aeiyoeo e?enoae?/i? c?acee nii/aoeo aeine?aeaeoaaeenue
oioiiaoiaeii. An? ?ic?aooiee cae?enithaaeenue ca aeiiiiiaith i?ia?aiiiai
caaacia/aiiy NSD (Nrystal Structure Determination). ?iaeaene
?ica?aeiino? (R)

aeey ia?aaaaeii? a?eueoino? no?oeoo? neeaaeaee 0.0260.072.

?yae e?enoae?/ieo eiiieaen?a oeio M(n-m)[CumXn] (M – K+, NH4+, Rb+,
Cs+; X — Cl, CN) i?iyaeythoue caeaoi?noue aei ethi?ianoeaioe??, cie?aia,
i?ae ae??th ?aioaai?anueeiai aai oeueo?ao?ieaoiaiai i?ii?iiy aiie
iiaeooue na?oeoeny /a?aiiei, caeaiei aai nei?i eieuei?ii; i?e/iio
ethi?ianoeaioi? aeanoeaino? a?aeiia?aeiiai c?acea caeaaeaoue ye a?ae
oeio I+, oae ? a?ae neeaaeo eiiieaeniiai ai?iio [CumXn](n-m)-.

?icae?e 4. E?enoaeio?i?y ?ioa?iaae?ao?a eoi?ieaoae?oe/iiai ia?aoai?aiiy
aoeaoeeaio oa eiai iio?aeieo.

?icae?e i?enay/aii e?enoaeio?i?/i?e oa?aeoa?enoeoe? no?oeoo?ii
aeine?aeaeaieo eiiieaen?a (oaae. 1), na?aae yeeo ai?iii?
eoi?iaaeiaai?aei? (inaaaeiaaeiaai?aei?) eiiieaene oeio M(n-m)[CumXn]
(X=Cl, Br, CN) (?? 1-13), ui ooaiththoueny ia ii/aoeia?e noaae??
i?ioeano ie?aiia?ecaoe?? (a?ae?ioe?aioaaiiy) N2I2 ? ?o no?oeoo?a a
ia?oiio iaaeeaeaii? a?aeia?aaeo? aoaeiao eaoae?caoi?a o aeo?aeiiio noai?
(?en. 1); i?ii?aei? eoi?ioei?eaei? (eoi?ioe?ai?aei?) eiiieaene c
aoeaoeeaiii (?? 14-20) oa i?iaeoeoaie eiai ia?aoai?aiiy (iiii-
(?? 21-33) ? aeecai?uaieie (?? 34, 35) iio?aeieie N2I2). Ine?eueee i?ae
/an ia?aa?ao ?aaeoe?? eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio oa eiai
iio?aeieo a ii/aoeiai neaaieeneiio na?aaeiaeu? nii/aoeo aeieeathoue
niieoee Nu(I) aoeaoeeai?aeiiai oeio (- aai ,-) (?en. 2 ? 3), a aaea
caiaeii (i?e cia/iiio cieaeaii? ?I) — -eiiieaene (?en. 4, 5 ? 6), a
iaaeao eiaeii? a?oie no?oeoo?ii aea/ai? niieoee ?ici?uai? ca niiniaii
eii?aeeiaoe?? ca`yceo NN (-, ,- oa -eiiieaene), ui aeicaiey? a?eueo
iiaii ioa?aeoa?ecoaaoe i?ioeane eiiieaeniooai?aiiy, ui a?aeaoaathoueny
ia ??cieo noaae?yo ?aaeoe??. A ?acoeueoao? i?iaaaeaieo

aeeoey 1.

E?enoaeia?ao?/i? oa?aeoa?enoeee aeine?aeaeaieo eiiieaen?a Nu(I) —
?ioa?iaae?ao?a (aai aiaeia?a) eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio
oa eiai iio?aeieo

?NiieoeaOei eii?-aeeiaoe??I?. a?.ZIa?aiao?e eii??ee (, a?aae.)V, 3*NN
ca`yceoa

()b

()c

()123456789eoi?iaaeiaai?aei?
(inaaaeiaaeiaai?aei?)1Hpy[CuCl2]—P21/m69.100(3)10.057(3)13.226(5)
112.59(2)11182Him[Cu2Cl3]—Pwmetafile8? ???????????????
???????????yyy????.????1?????????????
?a????&??yyyy?????ayIyA?I???&?
?MathType??????u????????????-????? ???????u0th??????98.43(4)7.243(4) 107.35(3)6.706(3) 90.12(4)4063Ns3[Cu2Cl5]—Cmcm415.4446(2)8.7528(2)8.6777(3)11734(NH4)2[Cu3 Cl51/3H2O1/15CuCl]—Iwmetafile8? ??????????????? ???????????yyy????.????1?????????????? ???&??yyyy?????ayNy?N???&? ?MathType??????u????????????-?????7? ????7?ae????u0th??????120.75(3)13.170(4)321511Rb11[Cu2(H2O)2][Cu15C l24 (CuIICl6)]—B2/m224.787(3)13.126(2)11.318(3) 122.36(1)311012K3[Cu(CN)4]1/2H2O—R3c69.6656(1)17.3625(3)140513NH4[Cu2(CN )3]H2O—P21/c411.932(5)8.376(3) 94.93(4)7.512(5)748Oaaeeoey 1. (i?iaeiaaeaiiy)123456789c aoeaoeeaiii14[K(H3O+)][Cu2(CN)2(CC)]; P21/b412.063(4)7.453(6)8.154(3) 97.23(2)72715(Him)4[Cu9Cl11(CCH)2]2C2/m112.563(3) 100.64(2)18.394(4)3.968(1)90116(Hpy)4[Cu9Cl12(CCH)]2B2/m219.798(9)7.980( 3)12.979(6) 105.77(2)197317(NH4)8[Cu29Cl29(CC)4]7H2O3, 2, 3; 2, 3, 3Pbam223.114(7)14.398(4)10.300(3)342818NH4[Cu3Cl4(INNI)]2Abm289.334(3)18 .407(5)10.581(5)181819Rb[Cu3Cl4(INNI)]2Abm289.388(3)18.514(5)10.607(5)18 4320NH4[Cu8Cl9(HCCH)4] 2/5[Cu(H2O)2][CuCl2]H2O2I4/mmm211.624(4)9.543(3)1289c oa?i?iaeueieie aee?iaie21Him[Cu4Cl4(CCCH2OH)]H2O2, 2Pwmetafile8? ??????????????? ???????????yyy????.????1????????????? ?a????&??yyyy?????ayIyA?I???&? ?MathType??????u????????????-????? ???????u0th??????97.24(2)7.688(2) 86.53(2)7.527(2) 101.97(2)71522NH4[Cu4Cl4(CCCH2OH)]H2O2, 2P21/a421.14(3)7.590(9)7.91(1) 109.5(1)118023(NH4)2[Cu4Cl5(CCCH2OH)]H2O2, 2Pwmetafile8? ??????????????? ???????????yyy????.????1?????? ????????a????&??yyyy?????ayIyA?I???&? ?MathType??????u????????????-????? ???????u0th??????89.46(2)10.269(2) 86.46(2)5.845(1) 99.18(2)69924(Han)2[Cu4Cl5(CCCH2OH)]2, 2P212121424.204(8)15.488(7)5.756(2)215825Cs2[Cu5Cl6(CCCH2OH)]2, 2Pwmetafile8? ??????????????? ???????????yyy????.????1????????????? ?a????&??yyyy?????ayIyA?I???&? ?MathType??????u????????????-????? ???????u0th??????93.29(5)7.217(4) 104.10(9)6.066(4) 81.47(7)75426Rb3[Cu7Cl9(CCCH2OH)]H2O3, 2P212121417.340(3)14.931(3)8.515(2)220527(Hpy)2[Cu8Cl8(CCCH2OH)2]H2O3, 2; 2, 2Pwmetafile8? ??????????????? ???????????yyy????.????1????????????? ?a????&??yyyy?????ayIyA?I???&? ?MathType??????u????????????-????? ???????u0th??????93.50(2)18.878(3) 79.22(2)8.901(3) 101.82(2)1404Oaaeeoey 1. (cae?i/aiiy)12345678928(Han)3[Cu8Cl10(CCCH2OH)]2H2O2, 2Pwmetafile8? ??????????????? ???????????yyy????.????1?????? ????????a????&??yyyy?????ayIyA?I???&? ?MathType??????u????????????-????? ???????u0th??????106.77(5)12.242(8) 92.05(6)11.341(7) 113.38(6)179629Hmea[Cu9Cl8(CCCH2OH)2(H2O)2]3, 2; 3, 2P21/n216.472(5)10.624(3)6.812(2) 100.90(3)117130Han[Cu2Cl3(HCCCH2OH)]2Pbca827.65(1)12.430(5)7.657(3)26303 12CuClHCCCH2OH2P21/a1220.059(5)15.187(5)6.196(2) 101.80(2)1847c aeeai?iaie32[Cu25Cl17(CCCH=NH2)8]14H2O2, 2I41/amd419.579(4)25.925(6)993933[Cu7Cl7(ICCCH=NH2)3]2P63213.444(4)6.219 (1)973343CuBr CH2=CHCH2CCCH2CH=CH2 (iiaeeo?eaoe?y A)P21/a415.197(6)11.784(5)6.893(3) 108.32(2)1172 353CuBr CH2=CHCH2CCCH2CH=CH2 (iiaeeo?eaoe?y A)Pca21420.769(6)8.582(3)6.823(3)1216 * Iaaaaeai? caie?oaeai? cia/aiiy ia`?i?a eii??ie. Oaaeeoey 1. aeine?aeaeaiue aia?oa anoaiiaeaii e?enoae?/io no?oeoo?o eiiieaen?a NuX (X=Cl, CN) c aoeaoeeaiii oa eiai oa?i?iaeueieie aiaeiaaie aoeaoeeai?aeiiai oeio (15 niieoe). Ia ?en. 7 iieacaii ni?aa?aeiioaiiy aea/aieo aaoi?ii eiiieaen?a ? a?aeiieo a e?oa?aoo??. ?en. 7. Ni?aa?aeiioaiiy /enea aeine?aeaeaieo aaoi?ii eiiieaen?a ? a?aeiieo ?ai?oa. ?icae?e. 5. Iniaeeaino? ooai?aiiy ca`yceo Cu(I)–(CC) a eoi?i-eiiieaenao N2I2 oa eiai iio?aeieo. Aeei?enoiaoth/e ?acoeueoaoe ?aioaaiino?oeoo?iiai aiae?co, i?iaaaeaiiai aeey iieaeoey?ieo oa ai?iiieo - ? ,-eiiieaen?a aaeiaai?ae?a eoi?oio(?) c aoeaoeeaiii, aee?iaie ? aeeai?iaie, ?icaeyaeathoueny iniaeeaino? oi?ioaaiiy eii?aeeiaoe?eii? noa?e Cu(I) oa aaiiao?e/i? ia?aiao?e -eii?aeeiiaaiiai e?aoiiai aoaeaoeue-aoaeaoeaaiai ca`yceo c iaoith ioe?iee aoaeoeaiino? aca?iiae?e eoi?oi(?) - e?aoiee ca`ycie N-N, a oaeiae ii??aiyiiy caeaoiino? a?oi N=N ? NN aei aca?iiae?? c Cu(I). A i?ioean? iane/aiiy eaoae?oe/iiai ?ic/eio nenoaie Iuetheaiaea aoeaoeeaiii, iieaeoee inoaiiueiai ca`ycothoueny c NuCl a eiiieaene. Aoeaoeeaiiaa a?oia caeaoia eaaei cai?uoaaoe aoiie Oei?o a no?oeoo?ao eoi?ioei?eaeieo eiiieaen?a, caaaeyee aeecueeino? aai-aea?-aaaeueniaeo ?aae?on?a aoii?a Nl i a?oi NN, ui ? aaaeeeaith ia?aaeoiiaith eoi?ieaoae?oe/iiai ii?aoai?aiiy aoeaoeeaio oa eiai iio?aeieo. A ?acoeueoao? oaeiai cai?uaiiy NN-ai?nia i?aai?/ia niieoea aeoeao?oueny aiane?aeie ooai?aiiy eiiieaeno c Nu(I), a yeiio aoii iaoaeo(?) aca?iiae?? c nenoaiith -aeaeo?ii?a iio??eiiai ca`yceo. I?e oeueiio a -eiiieaenao ci?iththoueny aaiiao?e/i? oa aia?aaoe/i? oa?aeoa?enoeee eii?aeeiiaaii? aoeaoeeaiiai? niieoee. Oea noi?iaiaeaeo?oueny aeaoi?iaoe??th aeo?aeiiai eii?aeeiaoe?eiiai iie?aae?a aoiia Iaoaeo a -eiiieaenao eoi?oio(?), yea, oaeei /eiii, aeicaiey? ioe?ithaaoe nooi?iue aeoeaaoe?? aoeaoeeaiiai? a?oie ia iaoae?/iiio oeaio??. A no?oeoo?ao aeeai?iiaeo eoi?iaaeiaai?aeieo -eiiieaen?a (?? 34 ? 35, oaae. 1) eii?aeeiaoe?eia ioi/aiiy -eii?aeeiiaaiiai c e?ioeaaith ieao?iiaith a?oiith aoiia Nu(I) i?aeoe/ii caaaeaee oi?io?oueny o aeaeyae? aeaoi?iiaaiiai a a?e o?eaiiaeueii? i??ai?aee oao?aaae?a (?en. 8, a), ui aeaco? ia iaaaeeeo aoaeoeai?noue -ca`ycoaaiiy Nu(I)–(C=C). Ia a?aei?io a?ae oeueiai aoii Iaoaeo -eii?aeeiiaaiee c a?oiith NN, yea a iieaeoe? aeeai?iiaiai e?aaiaeo caeia? aioo??oi? iieiaeaiiy (aeecai?uaiee aoeaoeeai), i?aeoe/ii caaaeaee ia?aaoaa? a ieinei-o?eaiiaeueiiio ioi/aii? (?en. 8, a), ui aeaco? ia cia/io aoaeoeai?noue -aca?iiae?? Nu(I)–(CC). Iniaeeaith iiaaae?ieith uiaei Nu(?) a?ae??ciy?oueny aoeaoeeai (?? 18-20, oaae. 1) oa eiai iiiicai?uai? iio?aei? (?? 30, 31 ? 33), a?oia NN yeeo a no?oeoo?ao eoi?ioei?eaeieo eiiieaen?a aeeiio? ?ieue i?noeiaiai -e?aaiaeo, iaeii/anii ca`ycoth/enue c aeaiia aoiiaie Iaoaeo (?en. 8, a). A?eueoa oiai, a oaeeo -eiiieaenao eeneee oa?aeoa? aoii?a I coiiaeth? ooai?aiiy aiaeiaaeo ca`yce?a oeio N–ICl, ye? a oe?eiio ni?eythoue noaa?e?caoe?? no?oeoo?e eiiieaen?a, i?e/iio oaeiai oeio aiaeiaa? ca`ycee oa?aeoa?ecothoueny aia?a??th, ni?aaei??iith c aia?a??th -aca?iiae??, ui ia iiaea ia iicia/aoeny ia aoaeoeaiino? inoaiiuei?. A no?oeoo?ao oeeo niieoe eiioaeoe N–ICl aeeeeeathoue aeiaeaoeiao iiey?ecaoe?th ca`yce?a Nu–Cl, ni?eyth/e oei naiei ci?oeiaiith -ca`ycoaaiiy o aoce? Cu(I)–(CC)–Cu(I), ui a naith /a?ao a?aeaeaa?oueny ia aaiiao??? -eii?aeeiiaaiiai iio??eiiai ?en. 8. Oeie eii?aeeiaoe?eiiai ioi/aiiy Nu(I) a -eiiieaenao NuCl i CuBr: a — o?eaiiaeueia i??ai?aea, i?eoaiaiia -eii?aeeiiaaiiio c? ca`yceii C=C aoiio Nu(I); a — ieinei-o?eaiiaeueia ioi/aiiy Cu(I) a -eiiieaenao c aeecai?uaieie iio?aeieie aoeaoeeaio; a — i?noeiaa -eii?aeeiaoe?y NN-ca`yceo aoiiaie Cu a -eiiieaenao N2I2 oa eiai iiiicai?uaieo iio?aeieo. ca`yceo N2I2. I?ae aeiaaeeiith aiaeiaaiai ca`yceo (N)–ICl ? aeaeiaaeaiiyi -eii?aeeiiaaiiai NN ca`yceo ?nio? iaaia caeaaei?noue: aeaeiaaeaiiy ca`yceo (N)ICl noi?iaiaeaeo? a?eueoa ?icoyaoaaiiy a?aeiia?aeiiai NN ca`yceo. Ia ?en. 9 aeuaiienaio oaiaeaioe?th cia?aaeaii a?ao?/ii, aea aeia?a aeaeii, ui aeiaaeeia -eii?aeeiiaaiiai ca`yceo NN iia`ycaia c a?aenoaiith ICl i?yiii?iii?oe?eiith caeaaei?noth. Oea coiiaeaia oei, ui aeaeo?iiiaeoeaioi?i? aoiie Oei?o /a?ac eiioaeoe (N)ICl caeaoi? nooo?ai aieeaaoe ia iiey?ecaoe?th ca`yce?a N–I -eii?aeeiiaaii? aoeaoeeaiiai? iieaeoee: /ei i?oei?oei (ei?iooei) aoaea aiaeiaaee ca`ycie (N)ICl, oei a?eueoa iiey?ecoaaoeiaoueny ca`ycie wmetafile8? ??°???????????? ???????????yyy????.????1?????? ???????` ???&??yyyy?????ayAy?"???&? ?MathType??????u0th?????? Ioaea, a ai?iiieo -eiiieaenao NuCl c aoeaoeeaiii oa eiai iiiicai?uaieie iio?aeieie aoaeoeai?noue -aca?iiae?? Nu(I)–(CC) caeaaeeoue a?ae aoaeoeaii? ?aae?caoe?? aiaeiaaeo ca`yce?a oeio (N)ICl, i?oei?noue yeeo cia/iith i??ith aeaoa?i?iiaaia oeiii ciai?oiueinoa?iiai eao?iio I+ (I= E+, Rb+, Cs+, NH4+, Him+, Hpy+, Han+, Hmea+), /a?ac ui inoaii?e ? ? aeoeaiei ni?aeiiiiiaioii eaoae?caoi?a ?aaeoe?? ie?aiia?ecaoe?? N2I2. * K[Cu3Cl4(C2H2)]; ** K[Cu8Cl9(C2H2)4]1/2HCu2Cl3H2O ?en. 9. Aca?iica`ycie a?aenoai? (N)ICl oa aeiaaeeie NN ca`yceo a -eiiieaenao NuCl c aoeaoeeaiii oa eiai iiiicai?uaieie iio?aeieie (e?i?eiee eiao?oe??io ei?aeyoe?? r =0.85). Ioia?aoe?y niieoe a?aeiia?aea? o?e, ui a oaae. 1. A ii/aoeiai iaeaea iaeo?aeueiiio aiaeiiio na?aaeiaeu? a i?enooiino? NuX (X=Cl, CN) aoeaoeeai oa eiai iiiicai?uai? iio?aei? ooai?ththoue eiiieaene aoeaoeeai?aeiiai oeio, a yeeo aoeaoeeai?ae-?ii iiaea eii?aeeioaaoenue c aoiiaie Iaoaeo ye - (?? 9, 14-16, oaae. 1), oae ? ,-niiniaaie (?? 17, 21-29, 33). Inoaii? oa?aeoa?ecothoueny cia/ii neeaaei?oith aoaeiaith, i?ae -eiiieaene. A no?oeoo?ao ,-eiiieaen?a Nu(I) ca`ycie NN iieaeoee aee?io iiaiaeeoue naaa ye i?noeiaee ,-e?aaiae, iaeii/anii -eii?aeeioth/enue aeaiia, a a no?oeoo?? ? 17 — iaa?oue o?ueiia aoiiaie Nu(I). I?e oeueiio aoaeoeai?noue -aca?iiae?? aeoaea caeaaeeoue a?ae niiniao -eii?aeeioaaiiy ca`yceo NN aoiiaie Iaoaeo. Ia a?aei?io a?ae -eiiieaen?a a eii?aeeiaoe?eiiio -aoce? Cu(?)–(CC)–Cu(I) ,-eiiieaen?a nei?i/aiiy a?aenoai? Cu-m (m — na?aaeeia ca`yceo NN), yea a iniiaiiio aecia/a?oueny aeiii?ii-aeoeaioi?iith neeaaeiaith -aca?iiae??, ia i?ecaiaeeoue aei iineeaiiy aeaoeaiiai ia?aiino, ? oiio ia aeeeeea? aeiaeaoeiai? aeaoi?iaoe?? o?eaiiaeueii-i??ai?aeaeueiiai ioi/aiiy Cu(I). A?eueoa oiai, a ,-eiiieaenao niinoa??aa?oueny cai?ioi?e aoaeo: a?eueo ei?ioe?e a?aenoai? Cu-m a?aeiia?aea? iaioa aeaeiaaeaiiy Cu-Laen. a eii?aeeiaoe?eiiio -aoce? Cu(I)–(CC)–Cu(I), ui coiiaeth?oueny neia?a?ciii aca?iiae?e Nu(I)–CC–R i Cu(I)–(CC). Inoaii?e iiaea i?iyaeyoeny a a?eueo?e aai iaio?e i???, a caeaaeiino? a?ae e?eueeino? ? i?inoi?iaiai ?icoaooaaiiy -ca`yce?a Nu–C. Noi?nia ,-eii?aeeiaoe?y ca`yceo NN coiiaeth? ooai?aiiy eeanoa??a [Cu4(CCR)] i [Cu5(CCR)] (aeey yeeo iaeei?iooa a?aenoaiue NuCu neeaaea? 2.455(4) ) c oe?eaaith noa?aio?i??th. A no?oeoo?ao eoi?ioei?eaeieo ,-eiiieaen?a c oa?i?iaeueieie iio?aeieie aoeaoeeaio aeyaeaii /ioe?e iniiai? oeie eeanoa??a (?en. 10), a?aei?iiino? a aoaeia? yeeo iieyaathoue o ??ci?e i???ioaoe?? aeaio aca?iii-ia?iaiaeeeoey?ieo -II (iieaeoey?ia i?a?oaeue) aoei?eueii? a?oie ,-eii?aeeiiaaii? /anoeiee –CCR a?aeiinii ieiueie ?, ui i?ioiaeeoue /a?ac ca`ycie NN. E??i oeeo /ioe?ueio oei?a eeanoa??a cono??/athoueny ? eiia?iiaai? oeie, iai?eeeaae, eeanoa? [Cu8] a no?oeoo?? ? 27, a yeiio oeie eeanoa??a ? ? ?V ia`?aeiothoueny i?noeiaei aoiiii Nu (?en. 10, ae), aai eeanoa? [Cu9] a no?oeoo?? ? 29, yeee ? eiia?iaoe??th aeaio eeanoa??a iaeiiai e oiai ae oeio ?V (?en. 10, a). A no?oeoo?ao ,-eiiieaen?a, a yeeo ?aae?co?oueny oei eeanoa?o ? (? 25), eiiieaia?ia ?icoaooaaiiy - ? -eii?aeeiiaaieo aoii?a Iaoaeo ? ca`yceo NN noai?th? aaiiao?e/i? ia?aaeoiiae aeey eooiaiai ia?ae?eaaiiy cacaeaieo d-i?a?oaeae aoii?a Nu(3) i Cu(4) (?en. 10, a) c aaea- ioieie *-II aoeaoeeaiiaiai ca`yceo. I?e oeueiio (Nu(I)CC–R)eoo-aeaoeaiee i?ioean noa? iano?eueee aoaeoeaiei, ui EI (eii?aeeiaoe?eiee iiiaia?aiiee) -ca`ycaieo aoii?a Nu(3) i Cu(4) (ye ? -eii?aeeiiaaieo aoii?a Nu(1) i Cu(2)) iaaoaathoue ieinei-o?eaiiaeueii? oi?ie. Neia?a?ci aca?iiae?e Nu(I)–CC–R ? Nu(I)–(CC) i?ecaiaeeoue aei iiey?ecaoe?? ca`yceo NN (N(1)–N(2)+), ui a?aeia?aaeo?oueny o iacia/iiio eiai aeaeiaaeaii?. ?ioa ea?oeia niinoa??aa?oueny o aeiaaeeo ?aae?caoe?? eeanoa?o oeio ?? (?en. 10, a). Ooo i?ioean a?aeoyaoaaiiy aeaeo?ii?a c canaeaieo d-i?a?oaeae -eii?aeeiiaaieo aoii?a Nu ia aaeaioi? *-II ca`yceo NN ? iaeiaoaeoeaiee, ine?eueee aea? -II aee?ia ?icoaoiao- ?en. 10. Oeie eeanoa??a, ui cono??/athoueny a no?oeoo?ao aoeaoeeai?aeieo eoi?ioei?eaeieo eiiieaen?a. thoueny ii a?aeiioaiith aei ii?iae? mn i?ae eooii 45i. A no?oeoo?ao ?? 21-24 EI -eii?aeeiiaaieo aoii?a Nu(I) caeeoathoueny oao?aaae?aie, oiae? ye -eii?aeeiiaaiei aoiiai Nu(I) aeanoeaa o?eaiiaeueii-i??ai?aeaeueia eii?aeeiaoe?y; i?e oeueiio niinoa??aa?oueny cia/ia aeaeiaaeaiiy ca`yceo NN aae aei 1.29(1) . Cia/iith aoaeoeai?noth (Nu(I)CC–R)eoo-aeaoeaiiai i?ioeano a?ae??ciythoueny oaeiae eiiieaene, a yeeo ?aae?cothoueny eeanoa?e oei?a ??? (?? 26 ? 32) ? ?V (? 28). A ieo - ? -eii?aeeiiaai? aoiie Nu(I) oa?aeoa?ecothoueny ia?aaaaeii ieinei-o?eaiiaeueiei ioi/aiiyi, a ca`ycie NN aeaeiaaeo?oueny iacia/ii. Iaeiae o oeueiio aeiaaeeo i?ioean a?aeoyaoaaiiy aeaeo?iiii? aonoeie c canaeaieo d-i?a?oaeae -eii?aeeiiaaieo aoii?a Iaoaeo (iniaeeai aoiia Nu(3)) cae?enith?oueny iaeii/anii aeaiia II (* ? *) a?oie NN, ine?eueee aeey oeueiai ? iaiao?aei? aaiiao?e/i? ia?aaeoiiae (?en. 10, a, a). Ia a?aei?io a?ae ai?ii?a –NNR, aoeaoeeai?ae-aeeai?ii –NN– iiaea -eii?aeeioaaoenue c aoiiaie Nu(I) a?ae?aco c aeaiia aoiiaie N. A no?oeoo?? ? 17 eiaeia c aeaio e?enoaeia?ao?/ii iacaeaaeieo /anoeiie N22– ae?? ye o?e/? i?noeiaee ,,-e?aaiae, niieo/ath/enue iaeii/anii c 8 aoiiaie Iaoaeo. I?eaa?oa? oaaao niin?a -eii?aeeioaaiiy aoii?a Nu(I) c aeaiia iacaeaaeieie /anoeieaie N22–. Eiaeai c aeaio aoii?a N a?oie N(3)N(4) ooai?th? -ca`ycee c o?ueiia aoiiaie Eoi?oio (?en. 11, a). Ca oaeeo ianoaaei aeaoeaiee i?ioean oeio (Nu(I)CCCu(I))eoo, /a?ac cia/iee ia?a?iciiae?e aeaeo?iiii? aonoeie a -aoce? Nu(I)–(CC)–Cu(I), iii?oii aieeaa? ia aaiiao??th -aocea (Nu-m-Cu = 106o). Iaeiae o aeiaaeeo /anoeiee N(1)N(2), aiane?aeie neia?a?cio aca?iiae?e Nu2–CC–Cu3 i Nu–(CC)–Cu, cao?aiiy aeaeo?iiii? aonoeie a -aoce? noa? iano?eueee a?ae/ooia, ui iio??eiee ca`ycie iaaoaa? ye?nii iiaeo aeanoeainoae ye -e?aaiae, i?iyaeyth/e caeaoi?noue aeiaeaoeiai -eii?aeeioaaoenue c o?ao?i aoiiii eoi?oio(I) (?en. 11, a). Ioaea, a no?oeoo?ao eeanoa?ieo aoeaoeeai?ae?a Nu(?) aia?oa aeyaeaii neia?a?/iee aoaeo -aca?iiae?? Nu(I)–CC–R, oi/i?oa ?? ceeaaeiai? a a ?en. 11. Eeanoa?e [Cu8(CC)] a no?oeoo?? ? 17. (Nu(I)CC)eoo-aeaoeaiiai i?ioeano, oa -ca`ycoaaiiy Nu(I)–(CC), yeee noi?iaiaeaeo?oueny /anii iacae/aeieie no?oeoo?ieie i?iyaaie ? iiyaith ye?nii iiaeo aeanoeainoae o -aeoeaiaaii? ia iaoae?/iiio oeaio?? aoeaoeeaiiai? a?oie. ?icae?e 6. No?oeoo?ia aeeiai?ea aca?iiae?? aoeaoeeaio oa eiai iio?aeieo c eiiieaenaie Nu(I) a eoi?ioei?eaeieo ?ic/eiao. Nie?ath/enue ia ?acoeueoaoe ?aioaaiino?oeoo?iiai aiae?co, i?iaaaeaiiai aeey e?enoae?/ieo eoi?iaaeiaai?aeieo eiiieaen?a (?? 1-11, oaae. 1), aea?oueny aiae?c aoaeiae ??cieo oei?a ai?ii?a [CumCln](n-m)–, ?icaeyaeathoueny aieea ciai?oiueinoa?iiai eao?iio I+ ia oi?ioaaiiy no?oeoo?e eoi?iaaeiaai?aeieo eiiieaen?a, a oaeiae no?oeoo?iee aniaeo aca?iiae?? ie?aieo ai?ii?a [CumCln](n-m)- c aoeaoeeaiiaeie niieoeaie. E?enoaeio?i?/iee aiae?c 23 no?oeoo?ii aea/aieo eoi?iaaeiaai?aeieo iai?aai?/ieo eiiieaen?a iieacaa, ui a ai?iiieo o?aaiaioao [CumOn](n-m)- aoiie Cu(I) iae/ano?oa ioi/othoueny /ioe?ia aoiiaie Nl aai Br ii oao?aaae?o; cono??/athoueny aoiie Nu ? c ieinei-o?eaiiaeueiei ioi/aiiyi, ??aeoa — c eooiaith aai e?i?eiith eii?aeeiaoe??th. A ai?iiao [CumOn](n-m)–, aei neeaaeo yeeo aoiaeeoue aeaa ? a?eueoa aoii?a Cu, EI inoaii?o iiaeooue niieo/aoenue i?ae niaith ii-??ciiio — aa?oeiaie, ?aa?aie ? iaa?oue a?aiyie. Iae/ano?oa cono??/a?oueny eiia?iiaaia anioe?aoe?y EI: iaeii/anii aa?oeiaie ? ?aa?aie. A aeayeeo aeiaaeeao caaaeyee eiia?iiaaiiio ii?aeiaiith EI aoii?a Cu ooai?ththoueny ea?eani? oeaie?oiiiae?ai? ai?iie [CumOn](n-m)–, a /eneaii? ii?iaeieie yeeo ca noaiith “a?noue-ainiiaea?” iiaeooue i?iieeaoe iieaeoee iaaaeeeeo ?ici???a (INNI, I2I, CuCCH oa ?io?) ? iaa?oue ie?ai? eiiieaene, iai?eeeaae, eiiieaen Cu(II) a no?oeoo?? ? 9 (?en. 1). Ia`?aeiaiiy EI aoii?a Cu ?aa?aie (a?aiyie) coiiaeth? aeieeiaiiy ei?ioeeo eiioaeo?a CuCu, aeanoeaeo eeanoa?ai. A ??ciiiai?oo? ?icaeyiooeo no?oeoo?ieo o?aaiaio?a i?iaeyaea?oueny no?eea oaiaeaioe?y aei ?o oneeaaeiaiiy a caeaaeiino? a?ae c?inoaiiy yaea?iino? ai?ii?a [CumCln](n-m)–. Aca?iica`ycie yaea?iino? o?aaiaioo [CumCln](n-m)– ? oa?aeoa?o i?noeiaiai aoiia Cl n (n = 1, 2, 3, 4) iiaeia cia?aceoe o aeaeyae? ae?aa?aie (?en. 12), aea aeia?a aeaeii, ui c?inoaiiy m ni?aiaaea? c iineeaiiyi i?noeiai? caeaoiino? aoii?a Nl. Oae, yeui i?e m = 1 ai?iiiei o?aaiaioai aeanoeaee aeineoue iecueeee nooi?iue anioe?aoe?? EI Cu(I), oi aaea i?e m = 2, 3, 4 aeieeathoue iaea?eueo neeaaei? no?oeoo?i? oi?ie ai?ii?a. Aeuaiienaiee oaeo aeia?a ocaiaeaeo?oueny ? c ?acoeueoaoaie i?iaaaeaieo ?ioeie aaoi?aie aeine?aeaeaiue uiaei ?ic/eiiino? CuCl a ?ic/eiao ICl. Ca?aeii c ieie na?aae an?o iayaieo a eiioeaio?iaaiiio ?ic/ei? CuCl ? NH4Cl ai?iiieo eiiieaen?a [CumCln](n-m)– (m = 15, n = 27) eiioeaio?aoe?y eiiieaen?a c m = 2, 3, 4 ? iaea?eueoith ? neeaaea? iaeaea 30% a?ae noie eiioeaio?aoe?e an?o eiiieaen?a. Ioaea, caeaoi?noue EI aoii?a Nu(?) ia`?aeioaaoenue a neeaaei? aaeiia?aoe [CumCln](n-m)– i?e m = 2, 3, 4 iaoiiaeth? aenieo eaoae?oe/io aeoeaiinoue eiioeaio?iaaieo aiaeieo ?ic/ei?a CuCl i MNl. ?en. 12. Aca?iica`ycie nooiaiy anioe?aoe?? eii?aeeiaoe?eieo iiiaia?aiiee?a aoii?a Iaoaeo (n-Nl) oa yaea?iino? ai?iio [CumCln](n-m)–. A naith /a?ao aoaeiaa eiiieaeniiai ai?iio [CumCln](n-m)– nooo?ai caeaaeeoue a?ae oeio ciai?oiueinoa?-iiai eao?iio I+, ui aa?a o/anoue o eiiiea-eniooai?aii?. Anoaiia-eaii, ui eao?iie NH4+ caeaoi? ooai?thaaoe c CuCl e?enoae?/i? eii-ieaene c iaaecae/aeii neeaaeieie no?oeoo?a-ie oeaie?oiiai oeio (? 4). ?o iiyao ni?e-/eith? oao?aaae?e/ia oi?ia eao?ii?a aiii?th, aca?iiae?y yeeo c ?iiaie Nl– ?aae?co?oue-ny /a?ac aiaeiaa? ca`yc-ee oeio (N)–HCl, ui iaaea? ?iiiiio ca`yco- aaiith I+Nl–iai?yi-eaiiai oa?aeoa?o. C o??? ae i?e/eie ooai?ththoueny aaeo?i? no?oeoo?e ?? 1, 2, 5, 6, ieine? eao?iie I?o+, Iim+ (oa Han+) yeeo /a?ac aiaeiaa? ca`ycee (N)HCl oaae ni?e/eiththoue iiyao neeaaeieo no?oeoo?. Cai?ia NH4Cl ia ENl i?ecaiaeeoue aei ooai?aiiy ai?iiieo eiiieaen?a E2[CuCl3] i K[CuCl2]1/2H2O, eao?iie E+ a yeeo iacaeaoi? ooai?thaaoe iai?yieai? ca`ycee c ?iiaie Nl–, /a?ac ui neeaaeiiai ii?aeiaiiy EI Nu(I) a oeeo no?oeoo?ao ia niinoa??aa?oueny. Iaeiae naia oeaie?oiiiae?ai? no?oeoo?e, ui oi?iothoueny c ie?aieo iie?aae??a aoii?a Nu, ia`?aeiaieo a aaeiia?aoe, ni?eythoue iaea?eueo iiai?e ii/aoeia?e ni?aoe?? aoeaoeeaio, ui iaiao?aeii aeey aeoeaaoe?? iio??eiiai ca`yceo eiai iieaeoee. Noeeuei?noue eao?ii?a NH4+ ? Rb+ aei ?ciii?oiiai cai?uaiiy a no?oeoo?ao aeayeeo eoi?iaaeiaai?aeieo eiiieaen?a, iai?eeeaae, a ? 4 ? ? 8, iaoiiaeaia aeecueeeie cia/aiiyie ?o ?iiieo ?aae?on?a. A eaoae?oe/ieo i?ioeanao eiiieaeniei ai?iiai [CumCln](n-m)– a?aeaiaeeoueny aaaeeeaa ?ieue, ine?eueee aanue iiaeaeueoee o?ae ia?aoai?aiiy N2I2 nooo?ai caeaaeeoue a?ae ?o aeo?aeii? aoaeiae. Ia i?eeeaae? e?enoae?/ii? aoaeiae ?ioa?iaae?ao?a, aeae?eaieo c nenoaie HanCl–CuCl–H2O–HCCCH2OH, aia?oa iieacaii, ye aeo?aeia no?oeoo?a eiiieaeno [CumCln](n-m)– aieeaa? ia iioaioe?eio ?aaeoe?eio caeaoi?noue i?ii?aeieo niieoe. Oae, aacaa?ai? e?enoaee eiiieaeno ? 5, ye? aeiaaeathoue c eiioeaio?iaaiiai iaeaea iaeo?aeueiiai aiaeiiai ?ic/eio 4 iie?a CuCl ? 3 iie?a IanCl, i?ney aaaaeaiiy a nenoaio INNNI2II oaeaeei ?ic/eiythoueny ? cai?noue ieo ooai?ththoueny aeiao? e?enoaee aoeaoeeai?aeiiai eiiieaeno ? 28. I?ae /an ia?aa?ao ?aaeoe?? 2(Ian)3[Cu4Cl7] (? 5) + INNNI2II + 2H2O = = (Ian)3[Cu8Cl10(NNNI2II)]2H2O (? 28) + 3IanCl + HNl (6. 1) no??iei cieaeo?oueny ?I na?aaeiaeua. A aiaeia?/ieo oiiaao, aea i?e iieueiiio ni?aa?aeiioaii? CuCl ? IanCl 2:1, iaea?aeo?oueny ?ioee aoeaoeeai?aeiee eiiieaen ? 24: 4CuCl + 2IanCl + INNNI2II = = (Ian)2[Cu4Cl5(NNNI2II)] (? 24) + INl. (6. 2) Iaeiae eiai e?enoaee i?e noiyii? a iaoi/iiio ?ic/ei? (?I2) c /anii cieeathoue ? cai?noue ieo c`yaeythoueny e?enoaee -eiiieaeno ? 30: (Ian)2[Cu4Cl5(NNNI2II)] (? 24) + INl = = Ian[Cu2Cl3(INNNI2II)] (? 30) + Ian[Cu2Cl3]. No?oeoo?iee aniaeo iienaiiai a ??aiyii? (6. 1) ia?aoai?aiiy noaiaoe/ii iieacaii ia ?en. 13. Noaiaeeieoeth eiiieaeniiai ai?iio [Cu4Cl7]3–n no?oeoo?e ? 5 o aeaeyae? niieo/aieo i?ae niaith EI aoii?a Nu cia?aaeaii ia ?en. 13 (o?a. a). I?e aeiaeaaaii? aei ?ic/eio eiiieaeno ? 5 i?iia?a?eiaiai nie?oo, iieaeoee inoaiiueiai (caaaeath/e ia cia/io iiey?ecaoe?th ca`yceo N–I o ii/aoeiaiio, aeecueeiio aei iaeo?aeueiiai, na?aaeiaeu?) ?ii?cothoueny ? eiaeiee c ?ii?a I+, ui i?e oeueiio c`yaey?oueny, aca?iiae?? c iaeiei ?c aoii?a Nl (caoo?eoiaaiee ia ?en. 13, o?a. a) ai?iio [Cu4Cl7]3–n, caoiiethth/e eiai a ?ic/ei o aeaeyae? INl. A ?acoeueoao? a?aeuaieaiiy aoiia Nl ieoaaae?e/ia ii?iaeieia, ui ciaoiaeeoueny ana?aaeei? aeo?aeiiai iae?iiie?aae?a (?en. 13, o?a. a), ia?aoai?th?oueny a eaaae?aoii-i??ai?aeaeueio, iaae? yei? ia ?en. 13 (o?a. a) ie?aneai? ioieoe?ii. A oeth ii?iaeieio c aieo iniiae eaaae?aoii? i??ai?aee aeey aca?iiae?? c aoiiaie Nu (ye? a ii?iaeiei? ooai?ththoue iao?eoeth [Cu4] o aeaeyae? aeaoi?iiaaiiai oao?aaae?a c iaeei?iooith a?aenoaiith NuNu 2.801(9) ) i?iieea? ?ii –NNNI2II ? i?ae aoei?eueiith a?oiith inoaiiueiai ? aoiiaie Iaoaeo iao?eoe? [Cu4] ooai?ththoueny 4 ca`ycee aeaio oei?a — , ? ,. Aiane?aeie oeueiai i?ae iae?iiie?aae?ii ai?iio [Cu4Cl7]3–n ? /anoeieith –NNNI2II anoaiiaeth?oueny ??aiiaaaeiee ia?ao?aeiee noai, cia?aaeaiee ia ?en. 13 (o?a. a); ca`ycee Nu–Cl, ui iineaaeththoueny, iicia/ai? ioieoe?ii. A naith /a?ao, ?ic?ea ca`yce?a NuCl ci?uo? anoaiiaeaio ??aiiaaao a a?e ooai?aiiy eeanoa?o [Cu4(NNNI2II)] (?en. 13, o?a. a) — neeaaeiaiai aeaiaioo eiiieaeniiai ai?iio niieoee ? 28. A no?oeoo?? inoaiiuei? ,-eii?aeeiiaaia a?oia NN eiaeiiai ?iio i?iia?a?e?th ? caoeniooith c on?o aie?a /ioe?ia aoiiaie Nu ana?aaeei? eaaae?aoii-i??ai?aeaeueii? ii?iaeieie, oiio -aoii Aoaeaoeth /anoeiee –NNNI2II /a?ac noa?e/i? cao?oaeiaiiy ia iiaea aooe ia`?eoii aeey aoaee c aieo aeaeo?io?eueiiai aaaioo — eao?iio I+. *a?ac oea e?enoaee niieoee ? 28 iiaeooue ye caaaiaeii aeiaai ia?aaoaaoe a eeneiio iaoi/iiio ?ic/ei? ? i?e oeueiio ia ?iceeaaeaoeny. ?en. 13. Noa?aio?i?/ia noaia ia?aoai?aiiy eiiieaeno (Ian)3[Cu4Cl7] (? 5) a (Ian)3[Cu8Cl10(NNNI2II)]2H2O (? 28) a i?enooiino? INNNI2II. Cian?i ?ioith noa?ainiaoeeo?/i?noth oa?aeoa?eco?oueny ?aaeoe?y (6. 2), no?oeoo?iee aniaeo yei? noaiaoe/ii cia?aaeaiee ia ?en. 14. ?en. 14. Noaia ooai?aiiy oa ia?aoai?aiiy e?enoae?a eiiieaeno (Ian)2[Cu4Cl5(NNNI2II)] (? 24) a Ian[Cu2Cl3(INNNI2II)] (? 30). A ooai?aii? aoeaoeeai?aeiiai eiiieaeno ? 24 aa?a o/anoue ai?ii [Cu2Cl3]–n (?en. 14, o?a. a), yeee ia? i?eioeeiiai ?ioo, i?ae [Cu4Cl7]3–n, aoaeiao. Oa?aeoa?iith iniaeea?noth eiai aoaeiae ? oa, ui EI aoii?a Cu niieo/athoueny i?ae niaith aeeeth/ii ?aa?aie, ooai?thth/e eaioethae [Cu2Cl3]–n, a iaaeao yeeo an? aoiie Iaoaeo ciaoiaeyoueny iaeaea a iaei?e ieiuei?; i?e oeueiio aeieea? nai???aeia iine?aeiai?noue ieineeo, aeecueeeo aei eaaae?aoii? oi?ie iao?eoeue n[Cu4] (?en. 14, o?a. a). I?e aaaaeaii? a nenoaio i?iia?a?eiaiai nie?oo /anoeia aoii?a Nl (caoo?eoiaaieo ia ?en. 14 (o?a. a)), ye ? a ?aaeoe?? (6. 1), ?cieiaaeueii cai?uothoueny a?oiaie NN ?ii?a i?iia?a?e?th, /a?ac ui ia eiaei?e iao?eoe? [Cu4] a?aeaoaa?oueny ye -, oae ? -eii?aeeiaoe?y /anoeiie –NNNI2II. Caaaeyee noi?niiio ,-eii?aeeioaaiith i?oei?noue aeayeeo ca`yce?a Nu–Cl ?noioii ciaioo?oueny ? i?ae eaioethaiaeie o?aaiaioaie [Cu2Cl3]–n oa /anoeieaie –NNNI2II anoaiiaeth?oueny ia?ao?aeia no?oeoo?a, cia?aaeaia ia ?en. 14 (o?a. a). Inoaoi/iee ?ic?ea ca`yce?a NuCl i?eaiaeeoue aei iiyae ai?iio [Cu4Cl5(NNNI2II)]2–n (?en. 14 (o?a. a), aeanoeaiai no?oeoo?? ? 24. Ooo -aoii N ?iio –NNNI2II, “iinaaeaeaiiai” caa?oo ieineiai eeanoa?a [Cu4], aaea ? eaaei aeinooiiee aeey iiaeeeai? aoaee c aieo eao?iia I+. Oea ni?ey? ia?a?iaeaeaiith aeo?aeiiai eaioethaiaiai o?aaiaioo [Cu4Cl5(NNNI2II)]2–n a ?ioee — [Cu2Cl3(INNNI2II)]–n, aeanoeaee -eiiieaeno ? 30 (?en. 14 (o?a. ae)), e?enoaee yeiai aeieeathoue a iaoi/iiio ?ic/ei? (?I2) cai?noue e?enoae?a niieoee ? 24. ?icae?e 7. Eoi?ieaoae?oe/ia ie?aiia?ecaoe?y N2I2 ia iniia? no?oeoo?ieo aeaieo. Ocaaaeueiaiiy io?eiaii? iaie no?oeoo?ii? ?ioi?iaoe?? (oaae. 1) oa aeai? e?iaoe/ieo aeine?aeaeaiue, i?iaaaeaieo ?ioeie aaoi?aie, aeicaieeee ae?eoe ianooiii? aeoiee uiaei iaoai?cio ia?aa?ao oe??? ?aaeoe??, yeee noaiaoe/ii cia?aaeaii ia ?en. 15. Ia ii/aoeia?e noaae?? i?ioeano, eiee aeo?aeia ?I eiioeaio?iaaiiai aiaeiiai ?ic/eio NH4Cl i CuCl neeaaea?  5, ooai?ththoueny ai?iii? eiiieaene oeio [CumCln](n-m)– (?? 1-11) — ?ioa?iaae?ao ?. Ia?o? ii?oe?? i?iiouaiiai e??cue ?ic/ei aoeaoeeaio i?ecaiaeyoue aei ooai?aiiy neiao?e/iiai aoeaoeeai?aeo, eiiieaeno ? 17 (?en. 2) — ?ioa?iaae?ao ??: [CumCln](n-m)– (?) + N2I2 wmetafile8? ??oe???????????? ???????????yyy????.????1????????????? ?`???&[email protected]???&? ?MathType??????u?th??????I?e oeueiio eeneioi?noue nenoaie no??iei c?inoa?. I?e iiaeaeueoiio iane/oaaii? nenoaie aoeaoeeaiii eiiieaen ? 17 iinooiiai ia?a?iaeaeo?oueny a ?ioa?iaae?ao I?? (eiiieaene ?? 15 ? 16): iia?eueii [CumCln-2(NN)](n-m)– (??) + N2I2 + 2I+ + 2Nl– 2[CumCln-1(NNI)](n-m)– (???) + 2I+, yeee a aeoaea eeneiio na?aaeiaeu? aeenioe?th? ca noaiith: [CumCln-1(NNI)](n-m)– (???) + I+ + Nl– wmetafile8? ??…???????????? ???????????yyy????.????1????????????? ????&??yyyy?????ayaya????&? [email protected]??????(?en. 15, noaae?y (7.1)). ??aiiaaaeia noaae?y ooai?aiiy ?ioa?iaae?aoo I??, ca?aeii e?iaoe/ieo aeaieo, ? aecia/aeueiith a ?aaeoe?? iaea?aeaiiy IAA ?en. 15. No?oeoo?iee aniaeo ?aaeoe?? eoi?ieaoae?oe/ii? ie?aiia?ecaoe?? aoeaoeeaio. Eaoae?caoi? Iuetheaiaea — aeoaea eiioeaio?iaaiee aiaeiee ?ic/ei 3 iie?a CuCl oa 2 iie?a NH4Cl (ii noo? oeae ?ic/ei i?e t 80o C ? ?icieaaii eoi?ioei?eaeieo eiiieaen?a [CumCln](n-m)–). Oiio iiaeia aaaaeaoe, ui aeeaei?e ii?yaeie no?oeoo?e iaeiiai c ?ic/eiaieo eiiieaen?a, iai?eeeaae, neeaaeo [Cu3Cl51/3H2O1/15CuCl]2–n (?ioa?iaae?ao ?) a?aeiia?aea? eiai aoaeia? a e?enoae?/iiio noai? (? 4). A no?oeoo?? oeueiai eiiieaeno ? eii?aeeiaoe?eii-iaiane/ai? aoiie Nu(1) c? niaoeeo?/iei ioi/aiiyi o aeaeyae? o?eaiiaeueii? i??ai?aee c iieaeoeith e?enoae?caoe?eii? aiaee a ?? aa?oei? (?en. 15, o?a. ?). I?e iane/aii? aeoaea eeneiai ?ic/eio eiiieaeno ? aoeaoeeaiii i?ioiaeeoue ?aaeoe?y (7.2): [CumCln](n-m)– (?) + N2I2 wmetafile8? ??oe???????????? ???????????yyy????.????1????????????? ?`???&[email protected]???&??MathType??????u?th??????a ?acoeueoao? yei? iieaeoee N2I2 ia?aoiaeyoue a aeoeaiaaiee noai, iaiao?aeiee aeey iiaeaeueoi? ie?aiia?ecaoe?? (?en. 15, o?a. ?V); a ooai?aiiio ?ioa?iaae?ao? ?V (?aeaioe/iiio ca aoaeiaith aei iaeiiai c -eiiieaen?a ?? 18-20) iieaeoea N2I2 noa? aeaeo?iiio?eii. I?e c?oeiaii? inoaiiuei? c ?iiii –NNI, ui aeieea? ia noaae?? (7.1), ooai?th?oueny ca ?aaeoe??th (7.3) [CumCln(N2I2)](n-m)– (?V) + –NNI wmetafile8? ??O???????????? ???????????yyy????.????1????????????? a`???&[email protected]»???&??MathType??????u?th?????? [CumCln(CH2=CHCCH)](n-m)– (V) ?ioa?iaae?ao V — -eiiieaen NuCl c IAA, a yeiio aoii Iaoaeo -eii?aeeio? iieaeoeo e?aaiaeo ii N=N-ca`yceo (?en. 15, o?a. V). Iiaeaeueoa iane/aiiy aoeaoeeaiii eaoae?oe/iiai ?ic/eio (oaiia?aoo?a na?aaeiaeua  80i N) aaaea aei aeo?niaiiy iieaeoeith N2I2 iieaeoee IAA c eii?aeeiaoe?eii? noa?e Cu(?): [CumCln(CH2=CHCCH)](n-m)– (V) wmetafile8? ??G??????????? ???????????yyy????.????1????????????? ?????&??yyyy?????ayOy`T???&? [email protected]??????(?en. 15, noaae?y (7.4)). Ooai?aiiy iieaeoee IAA noi?iaiaeaeo? cieaeaiiy eiioeaio?aoe?? ?ii?a I+ ia 1 iieue-aea., oiio i?ney i?eieiaiiy iaaeoiaeaeaiiy a nenoaio aoeaoeeaio ?ic/eiaiee IAA (?I3) ca`yco?oueny c ?ioa?iaae?aoii ? a ?ioa?iaae?ao VI — ,-eiiieaen [Cu25Cl17(CCCH=CH2)8]14H2O (? 32) (?en. 3): [CumCln](n-m)– (?) + IAA wmetafile8? ??oe???????????? ???????????yyy????.????1????????????? ?`???&[email protected]???&??MathType??????u?th?????? [CumCln-1(NNNI=NI2)](n-m)– (V?) + I+ + Nl–. C iaeyaeo ia c?inoaiiy eeneioiino? ?ic/eio ?ioa?iaae?ao VI iiaea ?iciaaeaoenue (ye ? ?ioa?iaae?ao ??? ia noaae?? (7.1)) c ooai?aiiyi ?ii?a –NNNI=NI2 aai ia?aoai?thaaoenue a -eiiieaen [Cu7Cl7(HNNNI=NI2)3] (? 33) (?en. 5). I?ae ?ioa?iaae?aoii ?V (?? 18-20) ? ?iiaie –NNNI=NI2, ye? i?ney ioieiaeaeaiiy eaoae?oe/iiai ?ic/eio ciiao iiaeooue ooai?thaaoe -eiiieaene oeio ?ioa?iaae?aoo V, (?en. 15, o?a. ?V ? V), anoaiiaeth?oueny aeeiai?/ia ??aiiaaaa, ui c /anii (5-7 ae?a) ci?uo?oueny a a?e ooai?aiiy aeea?i?eaoeaoeeaio (AeAA): [CumCln(N2I2)](n-m)– (?V) + –NNNI=NI2 wmetafile8? ??O???????????? ???????????yyy????.????1????????????? a`???&[email protected]»???&??MathType??????u?th?????? 2CuClAeAA (VII?)+ [Cum-2Cln-2](n-m)– (?en. 15, noaae?? (7.5)* ? (7.5)). O?i?ci ooai?aiiy AeAA ? aiaeia?/iee aei oiai, ui iieno? neioac IAA, i?ioa a?ae??ciy?oueny iaaiith niaoeeo?eith. Oae, a e?enoae?/i?e a?aooe? eiiieaena ? 4 (?ioa?iaae?ao ?) ?c o?eaiiaeueieo i??ai?ae c eaoae?oe/ii aeoeaiei aoiiii Cu(1) ana?aaeei? oi?io?oueny iao?eoey c a?aenoaiyie i?ae aeoeaieie oeaio?aie Nu(1)Cu(1) 7.9 , ui a?aeiia?aea? aeiaaeei? iieaeoee AeAA c S-o?aini?aeiith eiio?ao?aoe??th, yea nai?ie e?aei?ie N=N-ca`yceaie cae?enith? -eii?aeeioaaiiy oeeo aoii?a Nu(1) (?en. 15, o?a. VIII*). Aenia?eiaioaeuei? aeai?, ye? noinothoueny aoaeiae eoi?ioei?eaeieo eiiieaen?a AeAA neeaaeo 2CuClAeAA (?ioa?iaae?ao VIII) i 3NuClAeAA (?ioa?iaae?ao IX), a oaeiae aoaeiaa eiiieaen?a ?? 34 ? 35 (?en. 6) (aiaeia?a ?ioa?iaae?aoo IX), oea i?aeoaa?aeaeothoue. ?io? ie?aiia?e, cie?aia aoeaoeeai?eaeea?i?e (INNNI=NINI=NI2) ooai?th?oueny i?e c?oeiaii? ?iio –NNI c iieaeoeith IAA eiiieaeno ? 33, a oao?aia? aoeaoeeaio (NI2=NINNNI=NINI=NI2) — i?e aca?iiae?? eiiieaeno ? 33 c ?iiii –NNNI=NI2. I?ney a?aeaiiee AeAA eaoae?caoi? Iuetheaiaea ciiao iiaa?oa?oueny aei naiai aeo?aeiiai noaio (?en. 15, o?a I). Aeuaiienaiei ?iiiei iaoai?ciii iiynith?oueny ia eeoa ooai?aiiy ie?aiia??a N2I2, aea e ooai?aiiy ae?eeii?o?eeo a ?aaeoe?? a?ae?ioe?aioaaiiy N2I2. Aiaeia?/ii aei oiai, ye aoeaoeeaiiaee -eiiieaen NuCl (?ioa?iaae?ao IV) a eaoae?oe/i?e nenoai? Iuetheaiaea ca`yco?oueny c ai?iiii –NNI aai –NNNI=NI2 ? aea? a?aeiia?aeii IAA aai AeAA, c ?iiii –NN a?i ooai?th? ae?eeii?o?ee NI2=NI–NN. ?iie –NN, –NN– ? Cl– i?aeoe/ii iaeiaeia? ca ?ici??ii, oiio a eii?aeeiaoe?ei?e noa?? Nu(I) aiie iiaeooue ?cieiaaeueii cai?uoaaoe iaeei iaeiiai, oae ye oea ia? i?noea a no?oeoo?? eiiieaeno [E(I3I+)][Cu2(CN)2(CC)] (? 14), ooai?aiiy yeiai a?aeaoaa?oueny oeyoii cai?uaiiy iaei??? c o?ueio e?enoaeia?ao?/ii iacaeaaeieo /anoeiie –NN a ai?iiiiio oa?? [Cu2(CN)3]–n eiiieaena ? 13 ia ?ii –NN–. Iaaaaeaia aeua ia?aeiieeai ?ethno?o? caeaoi?noue eaoae?oe/ieo ?ic/ei?a nenoaie Iuetheaiaea (NH4Cl–CuCl(CuCN)–H2O) i?iyaeyoe aeoeai?noue ? a ?aaeoe?? a?ae?ioe?aioaaiiy aoeaoeeaio oa a aeayeeo ?ioeo nii??aeiaieo i?ioeanao. AENIIAEE 1.C aeiiiiiaith i?ea?iaeueiiai iaoiaeo ci?iiino?oiiiai aeaeo?io?i?/iiai neioaco (caoeuaiiai 2 iaoaioaie Oe?a?ie), a oaeiae aaciina?aaeiueith aca?iiae??th eiiiiiaio?a nenoaie IO–CuCl–H2O–L (M+ — eao?iie eoaeieo iaoae?a, aiii?th ? ?io? ii??a? eao?iie; O — Cl, Br, CN; L — CC-ai?nia niieoea) aia?oa aoei aeae?eaii o aeaeyae? ye?nieo iiiie?enoae?a ? ?aioaaiino?oeoo?ii aea/aii 35 niieoe — ?ioa?iaae?ao?a (aai ?o aeecueeeo iiaeaeueieo eiiieaen?a) eoi?ieaoae?oe/iiai ia?aoai?aiiy N2I2 oa eiai iio?aeieo, ui ooai?ththoueny ia ??cieo noaae?yo i?ioeano; c ieo 15 niieoe iaeaaeaoue aei eeano aoeaoeeai?aeieo eoi?ioei?eaeieo (eoi?ioe?ai?aeieo) eiiieaen?a. Iaea?aeaia no?oeoo?ia ?ioi?iaoe?y aeicaieeea aeyaeoe ?yae iniaeeainoae aoaeiae eii?aeeiaoe?eii? noa?e oeaio?aeueiiai aoiia, aecia/eoe aaiiao?e/i? ia?aiao?e aeoeaiaaii? ia iaoae?/iiio oeaio?? NN-ai?nii? iieaeoee, ioe?ieoe aoaeoeai?noue ? ooi/ieoe i?e?iaeo iaoae-e?aaiaeii? aca?iiae?? oa ?ioa?i?aooaaoe ?aaeoe?eio caeaoi?noue i?ii?aeieo eiiieaen?a ? aeoeai?noue eaoae?caoi?a.2.Anoaiiaeaii, ui a e?enoae?/ieo eoi?ioei?eaeieo eiiieaenao, no?oeoo?a yeeo a ia?oiio iaaeeaeaii? a?aeia?aaeo? aoaeiao eaoae?caoi?a o aeo?aeiiio noai?, ai?iii? o?aaiaioe [CumCln](n-m)– a i??o c?inoaiiy yaea?iino? ai?iio (m) i?iyaeythoue no?eeo oaiaeaioe?th aei oneeaaeiaiiy. Neeaaei? no?oeoo?i? oi?ie oa?aeoa?i? aeey ai?ii?a c m = 2, 3, 4 (iai?eeeaae, Him[Cu2Cl3], Cs3[Cu2Cl5], (NH4)2[Cu3Cl51/3H2O1/15CuCl] i (Han)3[Cu4Cl7]), eiioeaio?aoe?y yeeo a eaoae?oe/ieo ?ic/eiao nenoaie Iuetheaiaea ? ia?aaaaeath/ith. Caeaoi?noue eii?aeeiaoe?eieo iie?aae??a Nu(I) ia`?aeioaaoenue o neeaaei? oeaie?oiiiae?ai? ai?iii? aaeiia?aoe coiiaeth? aoaeoeai?noue eaoae?caoi?a Iuetheaiaea, ine?eueee naia oae? no?oeoo?e ni?eythoue iaea?eueo iiai?e ii/aoeia?e ni?aoe?? aoeaoeeaio, ui ? iaiao?aeiei aeey iiaeaeueoi? aeoeaaoe?? iio??eiiai ca`yceo eiai iieaeoee.3.Aeyaeaii, ui neeaae oa aoaeiaa ai?iio [CumCln](n-m)– nooo?ai caeaaeeoue a?ae oeio (?ici??o, neiao??? oa eiio?ao?aoe??) ciai?oiueinoa?iiai eao?iio I+, yeee ? neeaaeiaith ni?aeiiiiiaioe eaoae?caoi?a Iuetheaiaea (INl). Anoaiiaeaii, ui iaea?eueo neeaaei? no?oeoo?i? oi?ie ai?ii?a ii?iaeaeothoueny eao?iiaie NH4+ oa ooieoe?iiaeueii nii??aeiaieie c iei eao?iiaie i?ioiiiaaieo ai?i?a, aieiaiei /eiii caaaeyee ?o caeaoiino? iaaeaaaoe aeaeo?inoaoe/i?e aca?iiae?? I+Nl– iai?yieaii? i???ioaoe??. Neeaaeia oeaie?oiiiae?aia ea?eania no?oeoo?a aeieea? a ?acoeueoao? ii?aeiaiiy ai?ii?a [Cu3Cl5]2– c eao?iiaie NH4+ (eoa?/ia oaca eaoae?caoi?a Iuetheaiaea (NH4)2[Cu3Cl51/3H2O1/15CuCl]); ?? iiyao aeeeoothoue oao?aaae?e/i? eao?iie aiii?th, aca?iiae?y yeeo c ai?iiaie Nl– ?aae?co?oueny /a?ac iai?yieai? aiaeiaa? ca`ycee (N)HCl.4.?aioaaiino?oeoo?iee aiae?c aeae?eaieo c ii/aoeiai aeecueeiai aei iaeo?aeueiiai ?ic/eio nenoaie IanCl–CuCl–H2O–HCCCH2OH (Ian+ — eao?ii ai?e?i?th) e?enoae?/ieo ?ioa?iaae?ao?a aeicaieea anoaiiaeoe ca`ycie i?ae niiniaii eii?aeeioaaiiy aoii?a Iaoaeo oa?i?iaeueieie aee?iaie ? ?aaeoe?eiith caeaoi?noth ?ioa?iaae?ao?a (eoi?ioei?eaeieo aoeaoeeai?ae?a, ooai?aieo aca?iiae??th ai?ii?a [CumCln](n-m)– c I–NNR), yeee aecia/a?oueny aoaeiaith aeo?aeiiai eiiieaeniiai ai?iio [CumCln](n-m)–, oi/i?oa i?inoi?iaith i???ioaoe??th aeoeaieo iaoae?/ieo oeaio??a a ai?ii?. Oe?e aca?iiae?? ni?ey? caeaoi?noue a?oie NN ?cieiaaeueii cai?uoaaoe aoiie Oei?o a eii?aeeiaoe?eieo iie?aae?ao Nu(I).5.Aeoiaey/e c iao?e/ieo ia?aiao??a -eii?aeeiaoe?eieo iie?aae??a aoii?a Nu(I) oa aaiiao?e/ieo oa?aeoa?enoee -aeoeaiaaiiai ia iaoae?/iiio oeaio?? e?aoiiai N–N ca`yceo, ioe?iaii aoaeoeai?noue aca?iiae?? eoi?oi(?) — NN (/e N=N) oa caeaoi?noue inoaii?o aei aca?iiae?? c Nu(I). A?eueoa aoaeoeai?noue -aca?iiae?? Nu(I)–(CN), ii??aiyii c Nu(I)–(C=C), coiiaeth?oueny iayai?noth a iieaeoe? aee?io aeaio -II, ye? a i?ioean? -ca`ycoaaiiy c Cu(I) ?icuaieththoueny ia aea?, a?aei?ii? i?ae niaith ca aia?a??th II ( ? ), ui a e?ioeaaiio i?aenoieo ? aecia/a? ?aaeoe?eio caeaoi?noue aee?i?a a eoi?ieaoae?oe/ieo ?aaeoe?yo.6.Ia i?eeeaae? eoi?iaaeiaai?aeieo -eiiieaen?a NN-ai?nieo i?aai?/ieo niieoe aeyaeaii ?nioaaiiy aeaio ye?nii a?aei?iieo niinia?a -ca`ycoaaiiy a?oi NN c aoiiaie Nu(I), ye? oa?aeoa?ecothoueny ??ciith aoaeoeai?noth -aca?iiae??: (1) ca o/anoth iaeii/anii aeaio -II aee?ia a ooai?aii? -aocea Nu(I)–(CC); (2) aca?iiae?y ie?aii eiaeii? c aeaio -II ca`yceo NN, ui i?ecaiaeeoue aei iiyae i?noeiaiai -aocea Nu(I)–(CC)–Nu(I). A inoaiiueiio eiaeia c -II aoeaoeeaiiai? a?oie iiaiaeeoue naaa aiaeia?/ii aei aoeeaiiai?, aaoiiiiii eii?aeeioth/enue c iaeiei aoiiii Iaoaeo. Eiiia?aoe?y ae - ? -II noai?th? oiiae aeey ca?eueoaiiy aianeo ye aeiii?ii-aeoeaioi?ii?, oae ? aeaoeaii? eiiiiiaio, ui ? ? i?e/eiith a?eueo aoaeoeaiiai ca`ycoaaiiy Cu(I)–aee?i, aeanoeaiai aeey aeiaaeeo (1).7.A ai?iiieo -eiiieaenao CuCl c aoeaoeeaiii oa eiai iiiicai?ua-ieie iio?aeieie ia aoaeoeai?noue -aca?iiae?? Nu(I)–(CC), yea i?iyaey?oueny o aeaeiaaeaii? -eii?aeeiiaaiiai NN ca`yceo, /eiyoue cia/iee aieea aiaeiaa? ca`ycee oeio N–INl. Aeaeiaaeaiiy -eii?aeeiiaaiiai ca`yceo NN iia`ycaia c a?aenoaiith INl i?yii-i?iii?oe?eiith caeaaei?noth. Aoii Cl, aeaeo?iiiaeoeaioi?i? aeanoeaino? yeiai ?noioii caeaaeaoue a?ae neee oa iai?yieaiiai oa?aeoa?o ?iiii? aca?iiae?? I+Nl–, /a?ac aca?iiae?th (N)ICl caeaoiee nooo?ai aieeaaoe ia iiey?ecaoe?th ca`yceo N–I -eii?aeeiiaaii? iieaeoee oa?i?iaeueiiai aee?io. Caaaeyee oeueiio ia aoiiao N aeaeo?iiia aonoeia iiaea c?inoaoe aai ae cieaeoaaoenue, ui ? coiiaeth? a?aeiia?aeia ciaioaiiy aai ca?eueoaiiy aianeo Nu(I)(CC)-aeaoeaiiai ia?aiino, aiane?aeie /iai ca`ycie NN cacia? a?aeiia?aeii iacia/iiai aai ae nooo?aiai aeaeiaaeaiiy.8.Eeanoa?iei aoeaoeeai?aeai eoi?oio(?) i?eoaiaiiee aoaeo neia?a?cio - (Nu(I)–CC–R) i - (Nu(I)–(CC)) aca?iiae?e, yeee noi?iaiaeaeo?oueny iacae/aeieie no?oeoo?ieie i?iyaaie oa i?ecaiaeeoue aei iiyae ye?nii iiaeo aeanoeainoae o -aeoeaiaaii? ia iaoae?/iiio oeaio?? a?oie NN (a no?oeoo?? (NH4)8[Cu29Cl29(CC)4] 7H2O aeyaeaio caeaoi?noue aeeai?iio –NN– -eii?aeeioaaoenue iaeii/anii c o?ueiia aoiiaie Nu(I)). Iniaeeaa ?ieue a oe?e aca?iiae?? iaeaaeeoue (Nu(I)CCCu(I))eoo- (/e (Nu(I)CC–R)eoo-) aeaoeaiiio i?ioeania?.9.Nie?ath/enue ia ?acoeueoaoe ?aioaaiino?oeoo?iiai aiae?co, i?iaaaeaiiai aeey e?enoae?/ieo ?ioa?iaae?ao?a (eiiieaen?a I(n-m)[CumCln], -, ,- oa -eiiieaen?a NuCl c aoeaoeeaiii oa eiai iio?aeieie), ui ooai?ththoueny ia ??cieo noaae?yo eoi?ieaoae?oe/ii? ie?aiia?ecaoe?? N2I2, aeaii e?enoaeio?i?/ia o?aeooaaiiy ?aaeoe?? Iuetheaiaea. I?ioean iieno?oueny ?iiiei iaoai?ciii, aeaiaioa?iee aeo yeiai cae?enith?oueny ca noaiith i?e?aeiaiiy aei -aeoeaiaaii? ia iaoae?/iiio oeaio?? iieaeoee INNI a?aeiia?aeii ?iio –NNI (ooai?aiiy iiiia?i?eaoeaoeeaio) aai ?iio –NNNI=NI2 (ooai?aiiy aeea?i?eaoeaoeeaio), aea iaea?eueo eiia??iei i?noeai aoaee ? iaeei c aoii?a N, ia yeiio, caaaeyee ia?aaaaeath/iio ((Nu(I)(CC))-aeiii?ii-aeoeaioi?iiio ia?aiino, cina?aaeaeo?oueny cia/iee iiceoeaiee ca?yae +. Ooai?aiiy ae aeea?i?eaoeaoeeaio i?io?ea? noa?ainiaoeeo?/ii ye oaiieaoiee neioac.10.Aia?oa aeyaeaii (? i?aeoaa?aeaeaii iaoaioii Oe?a?ie), ui eiiieaeni? niieoee eoi?oio(?) oeio In-m[CumXn] (M+ — NH4+, K+, Rb+, Cs+; X — Cl, CN), ye? eaoae?cothoue ia?aoai?aiiy aoeaoeeaiiaeo niieoe, i?iyaeythoue oaeiae caeaoi?noue aei ethi?ianoeaioe??. A caeaaeiino? a?ae neeaaeo ? aoaeiae eiiieaeniiai ai?iio oa oeio eao?iio M+ e?enoaee eiiieaen?a (NH4)2[Cu3Cl51/3H2O1/15CuCl] (aai Rb9[Cu13Cl22 H3O+Cl-]), Cs3[Cu2Cl5] i K3[Cu(CN)4]1/2H2O i?ae ae??th ?aioaai?anueeeo aai oeueo?ao?ieaoiaeo i?iiai?a na?oyoueny a?aeiia?aeii /a?aiiei, caeaiei aai nei?i eieuei?ii.Iniiaiee ci?no ?iaioe aeeeaaeaii o ioae?eaoe?yo: 1. Iuoaee/ei A. I., Iunueeea I. A., Aenaeue?oae E. A., Iacon I. Ae. -Eiiieaenu iaaee(?) n aeeaieiaie. Neioac e e?enoaeee/aneay no?oeoo?a niaaeeiaiee oei?eaea e a?iieaea iaaee(?) n ieoaaeeai-1,7-eiii-4 ninoaaa 3CuXC8H10. // Eii?aeeiaoe. oeiey.– 1992.– O. 18, ? 9.– N. 985–991. 2. Iuoaee/ei A. I., Ia/a?neee A. E., Iunueeea I. A. -Eiiieaenu iaaee(?) n aeeaieiaie Neioac e e?enoaeee/aneay no?oeoo?a iiaie iiaeeoeeaoeee aeeaeeeeaoeaoeeaiiaiai -eiiieaena a?iieaea iaaee(?) ninoaaa 3CuBrN8I10 // Eii?aeeiaoe. oeiey.– 1993.– O. 19, ? 7. – N. 544-547. 3. Ieoae?/ei A. I., Ienuee?a I. A., Iacon I. Ae. Neioac oa e?enoae?/ia no?oeoo?a -eiiieaeno oei?eaeo i?ae?(?) c ae?ei?iia?a?eiaei nie?oii neeaaeo NuClC6H8O. // Oe?. o?i. aeo?iae.– 1993.– O. 59, ? 7.– N. 690-693. 4. Iuoaee/ei A. I., Iunueeea I. A., Aenaeue?oae E. A. Aoeaoeeai eae iinoeeiaue -eeaaiae: neioac e e?enoaeee/aneay no?oeoo?a niaaeeiaiey NH4Cu3Cl4N2I2. // Eii?aeeiaoe. oeiey.– 1993.– O. 19, ? 9.– N. 722-726. 5. Iunueeea I. A., Iuoaee/ei A.I. Eoi?ieaoaeeoe/aneay ?aaeoeey Iuetheaiaea a naaoa ?aioaaiianeeo eo/ae. // AEo?i. no?oeoo?iie oeiee.– 1994.– O. 35, ? 5.– N. 120-132. 6. Iuoaee/ei A. I., Aeiaye O., Iunueeea I. A. Neioac e no?oeoo?a eiiieaena Rb11[Cu15Cl16Br6(CuIICl6)CuCCH], niaea?aeauaai iiiiaoeaoeeaieae iaaee(?). // AEo?i. iai?aaie/aneie oeiee.–1995. – O. 40, ? 5.– N. 757-762. 7. Iuoaee/ei A. I., Iunueeea I. A., Aenaeue?oae E. A. Niaaeeiaiea NH4[Cu2(CN)3]H2O: neioac, e?enoaeee/aneay no?oeoo?a, ?ani?aaeaeaiea ca?yaeia ia aoiiao. // AEo?i. iai?aaie/aneie oeiee. –1996. – O. 41, ? 1. – N. 75-78. 8. Ieoae?/ei A. I. Aeine?aeaeaiiy aca?iiae?? oai?eae?eaoeaoeeaio c aaeiaai?aeaie i?ae?(?) iaoiaeaie aeaeo?io?i?/iiai neioaco oa ?aioaaiino?oeoo?iiai aiae?co. // Oe?. o?i. aeo?iae.– 1996. – O. 62, ? 1. – N. 39–44. 9. Ienuee?a I., Ie?eiee A., Ieoae?/ei A., Ai??oi?e ?. Iniaeeaino? -aca?iiae?? N=N ? NN-ai?nieo niieoe c nieyie i?ae?(?). // I?aoe? IOO. O ?.– Euea?a, 1997.– N 201-212. 10. Iuoaee/ei A. I., Aenaeue?oae E. A., Aeaauaeia A. I. Iniaaiiinoe no?iaiey eoae/aneeo eiiieaenia iaaee(?) ninoaaa (NH4)2Cu3Cl5 1/3H2O1/15CuCl e Rb9Cu13Cl22I3I+Nl–, ia?acothueony a nenoaia ICl–CuCl–H2O–INl (I= NH4+, Rb+). // AEo?i. iai?aaie/aneie oeiee.–1997.– O. 42, ? 3.– N. 410-414. 11. Iuoaee/ei A. I., Aeaauaeia A. I., Aenaeue?oae E. A. Neioac e ?aioaaiino?oeoo?iia enneaaeiaaiea eiiieaena Ns3Cu2Cl5. // AEo?i. iai?aaie/aneie oeiee.–1997.– O. 42, ? 7.– N. 1125-1127. 12. Iuoaee/ei A. I., Iunueeea I. A. ?aioaaiino?oeoo?iia enneaaeiaaiea eiiieaenia iaaee(?), ia?acothueony a nenoaia RbCl–CuCl–HCCCH2OH. // Eii?aeeiaoe. oeiey.– 1998.– O. 24, ? 8.– N. 596-601. 13. Ieoae?/ei A. I. Neioac oa e?enoae?/ia aoaeiaa -eiiieaeno RbCu3Cl4N2I2. // Oe?. o?i?/iee aeo?i. – 1998.– O. 64, ? 9.– N. 16-20. 14. Iuoaee/ei A. I. NN-Naycue i?iia?aeeiaiai nie?oa eae aeaaaeaeu iinoeeiaue ,-eeaaiae a eeanoa?iii niaaeeiaiee (NH4)2[Cu4Cl5(CCCH2OH)]H2O. // AEo?i. iai?aaie/aneie oeiee. – 1998.– O. 43, ? 10.– N. 1639-1643. 15. Iuoaee/ei A. I. ?aioaaiino?oeoo?iia enneaaeiaaiea acaeiiaeaenoaey CuCl n i?iia?aeeiaui nie?oii a ?anoai?ao oei?eaea eieaeacieey. // AEo?i. iai?aaie/aneie oeiee.–1998. – O. 43, ? 11.– N. 1840-1846. 16. Iuoaee/ei A. I., Iunueeea I. A. Aeieeaoeaoeeaiiaua -eiiieaenu iaaee(?). Oaiieaoiue neioac e no?oeoo?a niaaeeiaiee [Cu25Cl17(CCCH=NH2)8]14H2O e [Cu7Cl7(ICCCH=NH2)3]. // Eii?aeeiaoe. oeiey.– 1998.– O. 24, ? 12.– N. 939-945. 17. Iuoaee/ei A. I., Iunueeea I. A., Ai?aoiee A. A. -Eiiieaenu iaaee(?) n aoeaoeeaiiauie eeaaiaeaie. Neioac e e?enoaeee/aneay no?oeoo?a -eiiieaena oei?eaea iaaee(?) n i?iia?aeeiaui nie?oii ninoaaa 2CuClHCCCH2OH. // Eii?aeeiaoe. oeiey.– 1999.– O. 25, ? 1.– N. 65-69. 18. Iuoaee/ei A. I., Iunueeea I. A., Aeaauaeia A. I. Eeanoa?iua -eiiieaenu iaaee(?). Neioac e e?enoaeee/aneay no?oeoo?a ia?aiai -eiiieaena aeeaoeaoeeaieaea iaaee(?) ninoaaa NH4)8[Cu29Cl29(CC)4]7H2O. // AEo?i. iai?aaie/aneie oeiee. – 1999.– O. 44, ? 1.– N. 46-52. 19. Iuoaee/ei A. I., Iunueeea I. A., Aeaauaeia A. I. Aoeaoeeai eae iinoeeiaue -eeaaiae. Neioac e e?enoaeee/aneay no?oeoo?a niaaeeiaiey NH4[Cu8Cl9(N2I2)4]2/5[Cu(H2O)2][CuCl2]H2O. // AEo?i. iai?aaie/aneie oeiee.– 1999.– O. 44, ? 3.– N. 411-414. 20. Iuoaee/ei A. I. Eeanoa?iua aoeaoeeaieaeu iaaee(?). Neioac e no?iaiea eeanoa?iiai -niaaeeiaiey (AnI)2[Cu4Cl5(CCCH2OH)] (AnI+ — eaoeii aieeeiey). // Eii?aeeiaoe. oeiey.– 1999.– O. 25, ? 5.– N. 359-364. 21. Iuoaee/ei A. I., Iunueeea I. A. Aoeaoeeaieaeiua -eiiieaenu iaaee(?). Neioac e no?oeoo?a eeanoa?iiai niaaeeiaiey MeaH[Cu9Cl8(CCCH2OH)2(H2O)2] (MeaH+ — eaoeii iiiiyoaiie-aiiiiey). // Eii?aeeiaoe. oeiey.– 1999.– O. 25, ? 6. – N. 461-465. 22. Iuoaee/ei A. I., Iunueeea I. A. ?aioaaiino?oeoo?iia enneaaeiaaiea i?iaeoeoia acaeiiaeaenoaey oei?eaea iaaee(?) n i?iia?aeeiaui nie?oii a i?enoonoaee oei?eaea ie?eaeeiey. // Eii?aeeiaoe. oeiey.– 1999.– O. 25, ? 7.– N. 533-541. 23. Iuoaee/ei A. I., Iunueeea I. A. Eiiieaeniua aoeaoeeaieaeu iaaee(?). Neioac e no?iaiea eeanoa?iiai -niaaeeiaiey Cs2[Cu5Cl6(CCCH2OH)]. // AEo?i. iai?aaie/aneie oeiee.– 1999.– O. 44, ? 7.– N. 1127-1130. 24. Iaoaio ? 22769 A Oe?a?ia, IE? N09E 11/08. Ethi?iioi? c /a?aiiei, caeaiei aai nei?i na?o?iiyi / Ieoae?/ei A.I., Ienuee?a I.A. (Oe?a?ia); ?96062492; Cayae. 22.06.96; Iioae. 30.06.98; Athe. ? 3.– 4 n. 25. Iaoaio ? 25459 A Oe?a?ia, IE? N30A 7/12, N30A 7/14. Niin?a iaea?aeaiiy iiiie?enoae?a -eiiieaen?a aaeiaai?ae?a i?ae?(?) / Ieoae?/ei A.I., Ienuee?a I.A. (Oe?a?ia); ?95073217; Cayae. 10.07.95; Iioae. 30.10.98. 26. Iaoaio ? 25450 A Oe?a?ia, IE? N30A 7/12, N30A 7/14. Niin?a iaea?aeaiiy e?enoae?/ieo iiaeeo?eaoe?e eoi?iaaeiaai?aeieo -eiiieaen?a c ae?eueieie iio?aeieie / Ieoae?/ei A.I., Ienuee?a I.A. (Oe?a?ia); ?95083610; Cayae. 1.08.95; Iioae. 30.10.98. 27. Mys`kiv M.G., Osietchkin S.I., Mykhalitchko B.M. Structure peculiarities of copper(I) chloride -complexes with acetylene and its olefin derivatives. // Book of abstr. "Fourteenth European crystallographic meeting".– Enschede (Netherlands). – 1992.– P. 193. 28. Iuoaee/ei A. I., Ina/eei N. E., Iunueeea I. A. Iniaaiiinoe -acaeiiaeaenoaey aoeaoeeaia e aai ieaoeiiauo i?iecaiaeiuo n oei?eaeii iaaee(?). // Oac. aeiee. "VI Niaauaiey ii e?enoaeeioeiee iai?aaie/aneeo e eii?aeeiaoeeiiiuo niaaeeiaiee". – Eueaia.– 1992. – N. 48. 29. Ieoae?/ei A. I., Ienuee?a I. A. Eiiieaene i?ae?(?) oeio guest-host ia iniia? eoi?iaaeiaai?aeieo niieoe oeaie?oii? aoaeiae. // Oace aeii. "XIV Oe?a?inueei? eiioa?aioe?? c iai?aai?/ii? o?i??".– Ee?a.–1996. – N.77. 30. Ieoae?/ei A., Ienuee?a I. No?oeoo?ia o?i?y ?ioa?iaae?ao?a eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeai?a. // Ca??i. iaoe. i?aoeue Oinoi? iaoeiai? eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy-97”.– Euea?a.– 1997.– N. 9. 31. Iuoaee/ei A. I., Iunueeea I. A. E?enoaeee/aneea eiiieaenu iaaee(?) n oa?ieiaeueiuie aoeaoeeaiaie. // Oac. aeiee. "? Iaoeeiiaeueiie e?enoaeeioeie/aneie eiioa?aioeee".– *anoue. 1. – *a?iiaieiaea (?inney).– 1998. – N. 207. AIIOAOe?ss Ieoae?/ei A. I. No?oeoo?ia o?i?y ?ioa?iaae?ao?a eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio oa eiai iio?aeieo. ?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. – Euea?anueeee iaoe?iiaeueiee oi?aa?neoao ?iai? ?aaia O?aiea, Euea?a, 1999. Aeena?oaoe?y i?enay/aia aea/aiith no?oeoo?iiai aniaeoo eoi?ieaoae?oe/iiai ia?aoai?aiiy aoeaoeeaio oa eiai aiaeia?a, aacoth/enue ia ?acoeueoaoao ?aioaaiino?oeoo?iiai aiae?co e?enoae?/ieo ?ioa?iaae?ao?a, ui ooai?ththoueny ia ??cieo noaae?yo i?ioeano. C aeiiiiiaith i?ea?iaeueiiai iaoiaeo ci?iiino?oiiiai aeaeo?io?i?/iiai neioaco oa aaciina?aaeiueith aca?iiae??th eiiiiiaio?a c eaoae?oe/ii? nenoaie MX–CuCl–H2O–L (I — eao?iie eoaeieo iaoae?a, aiii?th ? ?ioeo i?ioiiiaaieo ai?i?a; O — Cl, Br, CN; L — NN-ai?nia i?aai?/ia niieoea) aia?oa aoee aeae?eai? o aeaeyae? ye?nieo iiiie?enoae?a ?ioa?iaae?aoe (aai aeecuee? iiaeaeuei? eiiieaene) eoi?ieaoae?oe/ii? ie?aiia?ecaoe?? (oa a?ae?ioe?aioaaiiy) N2I2 (35 eiiieaen?a); c ieo 15 niieoe — eoi?ioei?eaei? eiiieaene aoeaoeeai?aeiiai oeio. I?iaaaeaii ?aioaaiino?oeoo?ia aeine?aeaeaiiy an?o eiiieaen?a. E?enoaeio?i?/iee aiae?c io?eiaieo ?acoeueoao?a aeicaieea aeyaeoe ?yae iniaeeainoae aoaeiae eii?aeeiaoe?eii? noa?e oeaio?aeueiiai aoiia, aecia/eoe aaiiao?e/i? ia?aiao?e aeoeaiaaii? ia iaoae?/iiio oeaio?? NN-ai?nii? iieaeoee, ooi/ieoe i?e?iaeo iaoae-e?aaiaeii? aca?iiae?? ? ioe?ieoe ?? aoaeoeai?noue, ?ioa?i?aooaaoe ?aaeoe?eio caeaoi?noue i?ii?aeieo eiiieaen?a ? aeoeai?noue eaoae?caoi?a. No?oeoo?ii-o?i?/iee i?aeo?ae uiaei aoaeiae e?enoae?/ieo ?ioa?iaae?ao?a, ui ooai?ththoueny ia eiaei?e noaae?? i?ioeano, aeicaieea aea?aoe iaea?eueo eiia??iee (c e?eueeio iiaeeeaeo) ?iiiee iaoai?ci ie?aiia?ecaoe?? (a?ae?ioe?aioaaiiy) N2I2. Eeth/ia? neiaa: -eiiieaene Nu(I), aoeaoeeai?aei? eiiieaene Cu(I), aoeaoeeai, a?i?eaoeaoeeai, neioac, e?enoae?/ia no?oeoo?a, no?oeoo?ia o?i?y, ?aaeoe?y ie?aiia?ecaoe?? aoeaoeeaio. AIIIOAOeEss Iuoaee/ei A. I. No?oeoo?iay oeiey eioa?iaaeeaoia eoi?ieaoaeeoe/aneiai i?aa?auaiey aoeaoeeaia e aai i?iecaiaeiuo. ?oeiienue. Aeenna?oaoeey ia nieneaiea o/?iie noaiaie aeieoi?a oeie/aneeo iaoe ii niaoeeaeueiinoe 02.00.01 — iai?aaie/aneay oeiey.– Eueaianeee iaoeeiiaeueiue oieaa?neoao eiaie Eaaia O?aiei, Eueaia, 1999. Aeenna?oaoeey iinayuaia eco/aieth no?oeoo?iiai aniaeoa eoi?ieaoaeeoe/aneiai i?aia?aciaaiey aoeaoeeaia e aai aiaeiaia, iniiauaaynue ia ?acoeueoaoao ?aioaaiino?oeoo?iiai aiaeeca e?enoaeee/aneeo eioa?iaaeeaoia, ia?acothueony ia ?aciuo noaaeeyo i?ioeanna. N iiiiuueth i?eaeiaeueiiai iaoiaea ia?aiaiiioieiaiai yeaeo?ioeie/aneiai neioaca e iaiin?aaenoaaiiiui acaeiiaeaenoaeai eiiiiiaioia ec eaoaeeoe/aneie nenoaiu IO–NuCl–H2O–L (M — K+, Rb+, Cs+, NH4+, Him+ (eieaeacieee), Hpy+ (ie?eaeeiee), Ian+ (aieeeiee), Imea+ (iiiiyoaiieaiiiiee); O — Cl, Br, CN; L — HCCH, HCCCH=CH2, HCCCH2OH, CH2=CHCH2CCCH2CH=CH2) aia?aua auee auaeaeaiu a aeaea ea/anoaaiiuo iiiie?enoaeeia e no?oeoo?ii eco/aiu 35 niaaeeiaiee — eioa?iaaeeaoia (eeai aeeceeo iiaeaeueiuo eiiieaenia) eoi?ieaoaeeoe/aneie ieeaiia?ecaoeee (e aeae?ioeeaie?iaaiey) N2I2, ia?acothueony ia ?aciuo noaaeee i?ioeanna. Yoi — aieiiiua eoi?iaaeiaaieaeiua (inaaaeiaaeiaaieaeiua) eiiieaenu oeia I(m-n)[CumXn] (O=Nl, Br, CN) (13 niaaeeiaiee), eioi?ua ia?acothony a naiii ia/aea i?ioeanna au? aei ianuuaiey eaoaeeoe/aneiai ?anoai?a nenoaiu Iuetheaiaea aoeaoeeaiii, e eo no?oeoo?a a ia?aii i?eaeeaeaiee ioia?aaeaao no?iaiea eaoaeecaoi?a a enoiaeiii ninoiyiee; i?iiaaeooi/iua eoi?ioei?eaeiua (eoi?ioeeaieaeiua) eiiieaenu n naiei aoeaoeeaiii (7 niaaeeiaiee) e n i?iaeoeoaie aai i?aa?auaiey (iiii- — 13 eiiieaenia e aeecaiau?iiuie i?iecaiaeiuie C2H2 — 2 eiiieaena), n?aaee eioi?uo a iauae neiaeiinoe 15 eoi?ieiiieaenia i?aiaaeeaaeao e eeanno niaaeeiaiee aoeaoeeaieaeiiai oeia. E?enoaeeioeie/aneee aiaeec iieo/aiiuo ?acoeueoaoia iieacae, /oi yooaeoeaiay ?aaioa eaoaeecaoi?a Iuetheaiaea a ?aaeoeee ieeaiia?ecaoeee aoeaoeeaia (?aaii eae e a ?iaenoaaiiuo ?aaeoeeyo) iaoneiaeaia neeiiiinoueth nieae Nu(I) annioeee?iaaoueny a iieeyaea?iua aieiiu [CumNln](n-m)– ni no?oeoo?ie oeia guest-host e niiniaiinoueth a?oii NN ecieiaaeueii caiauaoue aoiiu Nl a yoeo eiiieaenao, /oi niinianoaoao eae yooaeoeaiie ni?aoeee aoeaoeeaia, oae e aai aeaeueiaeoae aeoeaaoeee. Onoaiiaeaii, /oi ninoaa e no?iaiea aieiiia [CumNln](n-m)– nouanoaaiiui ia?acii caaeneo io oeia (?acia?a, neiiao?ee e eiioeao?aoeee) aiaoianoa?iiai eaoeiia I+, yaeythuaainy nieiiiiiaioie eaoaeecaoi?a Iuetheaiaea (IO). Aunieay yooaeoeaiinoue -acaeiiaeaenoaey a eoi?ieiiieaenao aoeaoeeaieaeiiai oeia, ia?aciaaiea eioi?uo a eaoaeeoe/aneeo ?anoai?ao nenoaiu Iuetheaiaea (niaeanii eeiaoe/aneei aeaiiei) yaeyaony ii?aaeaeythuei aeey iiiaeo i?aa?auaiee N2I2, naycaia n acaeiiui oneeaieai ioaeaeueiuo oeiia acaeiiaeaenoaee — Nu(I)–CC–R e Cu(I)–(CC). Yoio, auyaeaiiue a eeanoa?iuo aoeaoeeaieaeao Nu(I), yooaeo neia?aecia niioaaonoaaiii - e -acaeiiaeaenoaee /anoi nii?iaiaeaeaaony iaiau/iuie no?oeoo?iuie i?iyaeaieyie e aicieeiiaaieai ea/anoaaiii iiauo naienoa a -aeoeae?iaaiiie ia iaoaeee/aneii oeaio?a a?oiia NN (a no?oeoo?a (NH4)8[Cu29Cl29(CC)4]7H2O iaia?oaeaia niiniaiinoue aeeaieiia –NN– -eii?aeeie?iaaoueny iaeiia?aiaiii aeaaea n o?aiy aoiiaie Nu(I)). No?oeoo?ii-oeie/aneee iiaeoiae a ioiioaiee no?iaiey e?enoaeee/aneeo eioa?iaaeeaoia, ia?acothueony ia eaaeaeie noaaeee eoi?ieaoaeeoe/aneiai i?ioeanna, iicaieee aua?aoue iaeaieaa aa?iyoiue (ec ianeieueeeo aeueoa?iaoeaiuo) iaoaieci ieeaiia?ecaoeee (aeae?ioeeaie?iaaiey) N2I2. I?ioeann iienuaaaony eiiiui iaoaieciii, yeaiaioa?iue aeo eioi?iai inouanoaeyaony ii noaia i?eniaaeeiaiey e -aeoeae?iaaiiie ia iaoaeee/aneii oeaio?a iieaeoea INNI niioaaonoaaiii eiia –NNI (iieo/aiea iiiiaeieeaoeaoeeaia), eiia –NNNI=NI2 (iieo/aiea aeeaeieeaoeaoeeaia) eee aea eiia –NN (iieo/aiea ae?eeiieo?eea); iaeaieaa aa?iyoiui ianoii ioeeaioeeueiie aoaee yaeyaony iaeei ec aoiiia N a?oiiu NN, ia eioi?ii (aneaaenoaea -naycuaaiey) aiciiaeii nin?aaeioi/aiea cia/eoaeueiiai iieiaeeoaeueiiai ca?yaea +. Eeth/aaua neiaa: -eiiieaenu Nu(I), aoeaoeeaieaeiua eiiieaenu Cu(I), aoeaoeeai, aeieeaoeaoeeai, neioac, e?enoaeee/aneay no?oeoo?a, no?oeoo?iay oeiey, ?aaeoeey ieeaiia?ecaoeee aoeaoeeaia. SUMMARY Mykhalichko B. M. Structural chemistry of the intermediates of cuprocatalytic conversion of acetylene and its derivatives. Manuscript. The Thesis for doctor of sciences degree by speciality 02.00.01 — inorganic chemistry. – Ivan Franko L`viv National University, L`viv, 1999. The thesis is devoted to studying of the structure aspect of cuprocatalytic conversion of acetylene and its analogues basing on X-ray structure data for the crystalline intermediates formed at various stages of the reaction. By means of the original alternating-current electrochemical technique or using a direct interaction of the components of MX–CuCl–H2O–L catalityc system (M — alkali metal cations, NH4+ and other protonated amines; X — Cl, Br, CN; L — CC-containing organic compound) qualitative crystals of the intermediates (or related model complexes) of the cuprocatalytic reaction of oligomerization (and hydrocyanation) of C2H2 were isolated at first (35 compounds) and structurally investigated. The 15 compounds of them belong to the copper(I) chloride complexes of acetylenide type. Crystallochemical analysis of the obtained results allowed to display some peculiarities of the construction of the central atom coordination sphere, to determine some geometric parameters of CC-containing molecule activated on the metallic centre, to define more precisely a nature of the metal-ligand interaction and to estimate its efficiency, and finally, to interprete a reaction ability of intermediate complexes as well as the catalyst`s activity. Structural chemistry approach to the obtained data on the intermediate complexes, appearing on each stage of the Nieuwland reaction, allowed to choose the most probable ionic mechanism (from several possible ones) of the oligomerization (hydrocyanation) of C2H2. Keywords: copper(I) -complexes, Cu(I) acetylenide complexes, acetylene, vinylacetylene, synthesis, crystal structure, structure chemistry, acetylene oligomerization reaction. I?aeienaii aei ae?oeo 26.10.99. Oi?iao 6084 1/16. Iai?? ionaoiee. Ae?oe ia ??cia?ao?. Oiiai. ae?oe. a?e. 2.33. Oiiai. oa?ai-a?aea. 2.21. Oe?aae 100 i?ei. Caiiae. ? 1512 AEI o??ia “AIN” I?iniaeo Naiaiaee, 12, i. Euea?a, oae. (0322) 72-19-64. 97-05-67

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