IAOeIIIAEUeIA AEAAeAIIss IAOE OE?A?IE

IINOEOOO OICEEI-I?AAII*II? OIII? OA AOAEAOIII?

(i. E.I.Eeoaeiaiea

Neiieii Na?aie Ieoaeeiae/

OAeE
541.49:546.742:546.922:546.924

NEIOAC OA ?AAEOeIEIA CAeAOIINOUe (- AIIIIEAOEEUeIIAI EIIIEAENO IEAOEIE
(IV).

02.00.03 I?aaii/ia oiiiy

Aaoi?aoa?ao

aeena?oaoei? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa oiii/ieo iaoe

Aeiiaoeuee-1998

Aeena?oaoei?th ? ?oeiien.

?iaioa aeeiiaia a Aeiiaoeueeiio aea?aeaaiiio oaoii/iiio oiiaa?neoaoi.

Iaoeiaee ea?iaiee: eaiaeeaeao oiii/ieo iaoe, noa?oee iaoeiaee
niia?iaioiee Iio/aiei Na?aie Aiaoieieiae/.

?inoeooo o?ceei-i?aai?/ii? o?i?? oa aoaeao?i?? IAI Oe?a?ie, noa?oee
iaoeiaee ni?a?ia?oiee.

Ioioeieii iiiiaioe: aeieoi? oiii/ieo iaoe, i?ioani? Ieieiee Ieeiea
Iaeneiiae/. Aeiiaoeueeee aea?aeaaiee oi?aa?neoao, caaiaeoaa/ eaoaae?e .

aeieoi? oiii/ieo iaoe, i?ioani? Iaeaaea Aeieo?i Ieoaeeiae/.
Aeiiaoeueeee aea?aeaaiee oaoii/iee oiiaa?neoao, i?ioani? eaoaae?e.

I?iaiaeia onoaiiaa — Aiaeaeie eaoaeico Oiceei-oiii/iiai iinoeoooo ii.
I.A.Aiaaonueeiai IAI Oe?a?ie, iinoi Iaeana.

Caoeno aiaeaoaeaoueny “ 10” a?oaeiy 1998 ?ieo i 14-00 aiaeeii ia
caniaeaiii niaoeiaeiciaaii? a/aii? ?aaee Ae 11.216.01 Iinoeoooo
oiceei-i?aaii/ii? oiii? oa aoaeaoiii? ii. E.I. Eeoaeiaiea IAI
Oe?a?ie /340114, i. Aeiiaoeuee, aoe. ?.Ethenaiao?a, 70./

C aeena?oaoei?th iiaeia iciaeiieoenue o aiaeiioaoei Iinoeoooo
oiceei-i?aaii/ii? oiii? oa aoaeaoiii? ii. E.I.Eeoaeiaiea IAI Oe?a?ie
/340114, i.Aeiiaoeuee, aoe. ?.Ethenaiao?a, 70./

Aaoi?aoa?ao ?icineaiee “ 27” aeiaoiy 1998 ?.

A/aiee nae?aoa? niaoeiaeiciaaii? a/aii? ?aaee

Ae 11.216.01
Oaiae?ee I.I.

AEOOAEUeIINOUe I?IAEAIE. Iiooe iiaeo eaoaeioe/ieo ?aaeoeie ?
aaaeeeaith caaea/ath a oai?i? oa i?aeoeoei oice/ii? i?aaii/ii? oiii?.
Oniio ooo cia/iith ii?ith coiiaeaii ciaiiyi oeyoia ooai?aiiy oa
iiaeaeueoiai ?iceeaaeo iioa?iaaeiaoia, yei /anoi ? iaoaeii?aaii/ieie
niieoeaie. Neioac iaoaeii?aaii/ieo niieoe ui ia iathoue noaaieicoth/eo
eiaaiaeia oa aea/aiiy ?o ?aaeoeieii? caeaoiinoi iiaea aeaoe eeth/a
aei ea?oaaiiy naeaeoeaiinoth eaoaeioe/ieo ?aaeoeie oa ooai?aiiy iiaeo
eaoaeioe/ieo nenoai. Iiai iiaeeeainoi a oeie aaeoci aiaee?eaa?
aeineiaeaeaiiy ?aaeoeie aoeeaeieiiieaenia ieaoeie oa ?o i?aaiiiioiaeieo
o aiaeieo ?ic/eiao. Inoaiiii /anii aeyaeaii, ui oaei i?aaii/ii
iioiaeii i?inoeo aoeeaeieiiieaenia ieaoeie ? iioa?iaaeiaoaie aaaaoueio
eaoaeioe/ieo i?ioeania, iai?eeeaae, eaoaeioe/ii? ooieoeiiiaeicaoei?
aeeaiia o nenoaii Pt(II)-Pt(IV), ioeeaioieueiiai caiiuaiiy a
aeeieaaeiaaiiaeao, aiae?ioei?oaaiiy aoeaoeeaio i?e eaoaeici PtCl42- oa
iioeo. Aeyaeaiiy ioeeaioieueieo aeanoeainoae eiiieaenia ieaoeie (II)
aeaei ciiao neioacoaaoe ?yae iaoaeii?aaii/ieo niieoe, ui aoee ?aiioa
iaaeinyaeieie, aai iaea?aeoaaeeny c aeoaea iaeei aeoiaeii. Iacaaaeath/e
ia oea, (-aiiiieaoeeueii eiiieaene ieaoeie (IV) ua e aeini —
aaaeeiaeinooiiee eean niieoe, neioac yeeo ? iaeii?th ic caaea/
i?iaaaeaiiai aeineiaeaeaiiy.

CA’ssCIE ?IAIOE C IAOEIAEIE I?IA?AIAIE, IEAIAIE, OAIAIE. ?iaioa
aiaeiiaiaea? iai?yieo aeineiaeaeaiue eaoaae?e caaaeueii? oiii?
Aeiiaoeueeiai aea?aeaaiiai oaoii/iiai oiiaa?neoaoo “Aeineiaeaeaiiy
eiiaoeee oa iaoaiicio ?aaeoeie ioeeaioieueiiai caiiuaiiy i?e
aeaeo?ioieueieo oeaio?ao”, ? aea?ae?a?no?aoei? A-50-90.

IAOA I CAAeA*I AeINEIAeAEAIIss.

-Neioac iiaiai eiiieaeno Pt (IV), ui ia? aiiiia?oio o (-iieiaeaiii aei
iaoaeioeaio?o.

-Aecia/aiiy iaoaiicio ieneaeaoeaiiai i?e?aeiaiiy ace?eaeeio aei
aoeeaeieiiieaenia Pt(II).

-Iiooe iiaeo oeyoia ?iceeaaeo iaoaeii?aaii/ieo iioiaeieo Pt(IV)

-Aecia/aiiy iaoaiiciia ciaiioiuei oa aioo?ioiueinoa?iiai aeiiiioaaiiy.

IAOEIAA IIAECIA IAeA?AEAIEO ?ACOEUeOAOIA. Aeyaeaii iiao ?aaeoeith
aeeiethaaiiy ieaoeie (II) aoeeaiiiiiii. Aeiaaaeaii, ui a nenoaii K2PtCl4
— aoeeaiiiii — HCl aiaeaoaa?oueny ieneaeaoeaia i?e?aeiaiiy i?ioiiiaaiiai
ace?eaeeio c ooai?aiiyi (-aeeieueiiai iioiaeiiai Pt (IV), o yeiai iiai,
aiaeiiiii aiae ?aiioa iaea?aeaieo (-aeeieueieo niieoe ieaoeie (IV),
yeinoi. Aeyaeaii aianie o ?aaeoeith eiiieaenia PtCl2(H2O)2,
PtCl3(H2O)-, a oaeiae PtCl42-. Aeiaaaeaii, ui eiiaoeea ?aaeoei?
aiaeiiaiaea? SN2- iaoaiicio.

Neioaciaaii iiaee (-aiiiieaoeeueiee eiiieaen ieaoeie (IV), yeee ia
iinoeoue o nai?io neeaaei noaaieicoth/eo eiaaiaeia.

Iieacaii, ui eiiaoeea ciaiioiueinoa?iiai ?iciaaeo aiaeiiaiaea?
iaoaiicio, yeee aeeth/a? SN2 — aoaeo oei?eae-aiiiio ia (-aoii aoaeaoeth
o?ain-Pt(CH2CH2NH3)Cl4(H2O) oa aaaea aei (-oei?aiiiiaoaio oa PtCl42-.

Aeyaeaii oa aeineiaeaeaii iiao ?aaeoeith aioo?ioiueinoa?iiai
aiaeiiaiiai aeiiiioaaiiy: aaoa?ioeeeeicaoeiy (-iaoaeieiiieaeniiai
iioiaeiiai aoeeaiiio ca ?aooiie aioo?ioiueiiieaeoey?ii? ioeeaioieueii?
aoaee NH2-a?oiith (-aoiio aoaeaoeth iaoaeieiiieaeno c ooai?aiiyi
aoeeaiiiiio ye ia?ainiiai i?iaeoeoo. Iieacaii, ui ye o aeiaaeeo
ciaiioiueinoa?iiai ?iciaaeo, oae i i?e aioo?ioiueinoa?iie oeeeeicaoei?
aiaeaoaa?oueny noaaieicaoeiy iaoaeii?aaii/ii? niieoee, ui iinoeoue
(-ca’ycie ieaoeia — aoaeaoeue ca ?aooiie eii?aeeiaoei? eiaaiaeo a
o?ain-iieiaeaiiy aei i?aaii/iiai o?aaiaioo ia?iceeaaeaii? /anoeie
eiiieaeno.

Neioaciaaii iiaee iaoaeioeeee — eiioeaao niieoeo ?aaeoei?
aioo?ioiueinoa?iiai aiaeiiaiiai aeiiiioaaiiy.

Aeyaeaii iiao ?aaeoeith (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV) o
aiaeieo eiaeeaeieo ?ic/eiao c ooai?aiiyi aoeeaio. Aeiaaaeaii, ui
iaoaiici oei?? ?aaeoei? aiaeiiaiaea? noaii, yea aeeth/a? iiia?aaei?
eiiieaiaioa?ia aiaeiiaeaiiy ii/aoeiaiai eiiieaeno aei aiaeiiaiaeiiai
iioiaeiiai ieaoeie (II) c iiaeaeueoei eiai ?iceeaaeii ia aoeeai oa
aoeeaeieiiieaen Pt(II).

I?AEOE*IA CIA*AIIss IAeA?AEAIEO ?ACOEUeOAOIA.

Aeyaeaia ?aaeoeiy ieneaeaoeaiiai aiiiiaoeethaaiiy iiaea aooe aeei?enoaia
o eaai?aoi?iie i?aeoeoei aeey neioaco aaaeeiaeinooiieo aiiiiaoeeueieo
niieoe ieaoeie (IV). Aioo?ioiueinoa?ia aeiiiioaaiiy aea? ciiao
neioacoaaoe iaoaeioeeeee, yei iaiiaeeeai iaea?aeaoe iioei oeyoii.

Io?eiaii eiiaoe/ii ?acoeueoaoe c aiaeoai?aiiy oa ?iceeaaeo
iaoaeii?aaii/ieo niieoe iiaeooue aooe aeei?enoaii aeey iiooeo iiaeo
aiiiaaiii-eaoaeioe/ieo nenoai.

Iaea?aeaii iaoaeii?aaii/ii niieoee iiaeooue aooe aeineiaeaeaii ye
iioaioeieii i?ioeiooeeiii i?aia?aoe.

INIAENOEE AIANIE CAeIAOAA*A. Iinoaiiaea, iiaeaioiaea, cia/ia /anoeia
aenia?eiaioo, ia?iaea ?acoeueoaoia oa /anoeiai ?o iioa?i?aoaoeiy
aeeiiaii aaciina?aaeiuei aaoi?ii ?iaioe Neiieiiei N.I. Iniaenoi aaoi?ii
aoee caeieniaii: iiaeaioiaea oa i?iaaaeaiiy eiiaoe/ieo aeineiaeaeaiue,
ia?iaea io?eiaieo ?acoeueoaoia ia AII. Aaoi?ii caeieniaii neioace
iaoaeieiiieaenia, ui iienaii a ?iaioi, ?o aeaeieaiiy oa i/enoea, a
oaeiae i/enoea anio aeoiaeieo niieoe aei iaeaaeiiai nooiaiy /enoioe.

Niiaaaoi?e iioaeieiaaieo ?iaio c oaie aeena?oaoei?: N.A. Iio/aiei —
iaoeiaee ea?iaiee, ieaioaaiiy aenia?eiaioo, iaaiai?aiiy oa
iioa?i?aoaoeiy ?acoeueoaoia; ?.A. Aicaa?o — iaaiai?aiiy ?acoeueoaoia;
A.A. Caiaueeia — iaaiai?aiiy ?acoeueoaoia oa iioa?i?aoaoeiy; A.I.
Aaeiae/aiei — ssI?-aeineiaeaeaiiy; A.I. Aiuoea — neioac aeoiaeieo
niieoe.

AI?IAAOeIss ?IAIOE. Iniiaii ?acoeueoaoe ?iaioe aeiiiaiaeaeenue oa
iaaiai?thaaeenue ia V Ananithciie eiioa?aioei? c iaoaeii?aaii/ii? oiii?
(?iaa, 1991?.), Ananithciie ?aaei “Iaoaiicie ?aaeoeie ioeeaioieueiiai
caiiuaiiy oa i?e(aeiaiiy” (Aeiiaoeuee, 1991?.) oa III eiioa?aioei?
iieiaeeo a/aieo-oiiieia (Aeiiaoeuee, 1991?).

IOAEIEAOeI? . Ca iaoa?iaeii aeena?oaoei? iaae?oeiaaii 6 ?iaio oa
oace o?ueio aeiiiaiaeae ia eiioa?aioeiyo.

NO?OEOO?A OA IANssA ?IAIOE. Aeena?oaoeiy aeeeaaeaia ia 128 noi?iieao
ae?oeiaaiiai oaenoo i neeaaea?oueny ic anooio, 5 ?icaeieia, caeeth/aiiy,
aeniiaeia, ia?aeieo oeeoiaaii? eioa?aoo?e ic 129 iaeiaioaaiue, iinoeoue
16 oaaeeoeue oa 21 ?enoiie.

IENEAeAOEAIA I?E?AeIAIIss ACE?EAeEIO AeI OEI?EAeIEO EIIIEAENIA
IEAOEIE (II)

Aiaeiii, ui aca?iiaeiy eiiieaenia ieaoeie, cie?aia aoeeaeieiiieaenia
oeio K2PtCl4 c aoeeaiiiiiii (ace?eaeeiii — Az) o iaeo?aeueieo aiaeieo
?ic/eiao aaaea aei i?iaeoeoia, ui iinoyoue eiaaiaeii aoeeaiiiii.
A?aoiaoth/e, ui aoeeaeieiiieaene ieaoeie (II), cie?aia PtCl42-, ?
iaoaeioeaio?iaaieie ioeeaioieaie e eaaei ?aaaothoue ca SN2 — iaoaiiciii
c aeeieoth/eie ?aaaaioaie RX (R = I, OSOMe oa ii.), oeieaai aeyaeoe
iiaeeeainoue iioiai oeyoo aca?iiaei? ieaoeie (II) c aoeeaiiiiiii, a
naia: ?ice?eooy ace?eaeeiiaiai oeeeeo aianeiaeie SN2 — aoaee ieaoeie
(II) ia aoii aoaeaoeth. Aeienii, ie ciaeoee, ui ca oiiaao i?ioiioaaiiy
ace?eaeeio (pKa = 7.8-8.0) aiaeaoaa?oueny ieneaeaoeaia i?e?aeiaiiy
aiaeiiaiaeii aei ?iaiyiiy

(1)

Caniaii II?-niaeo?ineiii? aeiaaaeaii, ui io?eiaiee eiiieaen (1a)
iinoeoue (-ca’ycie ieaoeia — aoaeaoeue oa ? ?aeeiei ieaoeii-i?aaii/iei
i?iaeoeoii ?aaeoei?. Anoaiiaeaii, ui (1a) ooai?th?oueny i?e aca?iiaei?
ace?eaeeio eeoa c oao?aoei?eaeiei aiiiiii, eiiieaene PtCl3(H2O)- oa
PtCl2(H2O)2 — ia aeoeaii. Cia/aiiy aia?ai? aeoeaaoei? oa
i?aaeaeniiiaioeieiiai iiiaeieea ?aaeoei? (1) (70,5 eAeae/iieue;
1.11(109 M-1 n-1) aeecueei aei io?eiaieo ?aiioa aiaeiiaiaeieo cia/aiue
(84 eAeae/iieue; 1.6(1011 I-1 n-1) aeey SN2 — aeeiethaaiiy ieaoeie (II)
aeeiaoeenoeueoaoii. Aea aiie ?icei aiae?iciythoueny aiae cia/aiue (22.4
eAeae/iieue; 400 I-1 n-1), anoaiiaeaieo i?io. Caiaueeiaei A.A. oa ni.
aeey ieneaeaoeaiiai i?e?aeiaiiy MeI aei o?eoei?eaeiiai eiiieaeno
PtCl3(H2O)-, ui aiaeaoaa?oueny ca o?ueiooeaio?iaei iaoaiiciii. Ua iaeei
aaaeeeaee a?aoiaio ia ei?enoue SN2-iaoaiicio ieneaeaoeaiiai i?e?aeiaiiy
ace?eaeeio aei ieaoeie (II) — ?icea cieaeaiiy ?aaeoeieii? caeaoiinoi i?e
ia?aoiaei aiae oao?aoei?eaeieo aei iaio ioeeaioieueieo aeaaoei?eaeieo
eiiieaenia, oeiiaa aeey aaea aeineiaeaeaieo SN2 -?aaeoeie aeeiethaaiiy
ieaoeie. Ineieueee cia/aiiy k eeoa?oueny i?aeoe/ii iaciiiiei i?e
aa?ithaaiii [H+] o iioa?aaei 0,3-0,9 I iiaeia c?iaeoe aeniiaie, ui
noano?ao aoaeo? ieaoeio (II) o i?ioiiiaaiie oi?ii.

Oaeei /eiii, aoeeaiiiii c eiiieaenaie ieaoeie (II) o aiaeieo ?ic/eiao
a caeaaeiinoi aiae eeneioiinoi na?aaeiaeua iiaea ?aaaoaaoe a aeaio
?icieo iai?yieao: o aiaenooiinoi eeneioe aca?iiaeiy aoeeaiiiiio c
K2PtCl4 i?ecaiaeeoue aei o?eaiaeueiiai caiiuaiiy oei?eaeieo eiaaiaeia
ia ace?eaeei. O eeneiio na?aaeiaeui, aianeiaeie ia?aoai?aiiy Az o AzH+
oaea ?aaeoeiy iaiiaeeeaa, a SN2 — aoaea aeiaiiiio PtCl42- i?ecaiaeeoue
aei ?ice?eooy ace?eaeeiiaiai oeeeeo c ooai?aiiyi i?iaeoeoo
ieneaeaoeaiiai i?e?aeiaiiy.

I?iaeoeo ?aaeoei? (1a) aoa aeaeieaiee a aiaeioe/ii /enoiio noaii

Iaea?aeaii, % N — 5.1; H — 1.6; N — 2.9; Cl — 36,9;

Ia/eneaii aeey KPtCl5(CH2CH2NH3), % N — 5.26; H — 1.55; N -3.07; Cl —
38.83).

I*-niaeo? eiiieaeno (ni-1; oaaeaoea c KBr): 3190 (((NH) 0.2, n); 2920
(((CH), anei., na?.); 2850 (((CH), nei, ae.ne.); 1560 (((NH), n); 1470
(((CH), ae.n); 411 (eiiai?ii ((Pt — C), ne.)

OO — niaeo? o ?ic/eii 0.1 M NaCl oa 0.4 M HClO4: (max = 263 ii ( =
5700 iieue-1 e ni-1; O 4 M HCl: (max = 263 ii ( = 6800 iieue-1 e ni-1

II?-niaeo? ?ic/eio [Pt (CH2CH2NH3)Cl5)]- o 3 I DCl: aeaa o?eieaoe
3J(HH) = 5.9 Aoe, ui iathoue oa?aeoa?ii ieaoeiiai naoaeioe ((H() = 3.94
i./. 2J(195Pt — H) = 81.3 Aoe; ((H() = 2.75 i./.; 3J(195Pt — H) = 26.4
Aoe.

Aeacaii ieaoeiiai naoaeioe naiae/aoue i?i iayaiinoue (-ca’yceo ieaoeia —
aoaeaoeue.

O aiaenooiinoi DCl ia?aiao?e niaeo?o aiae?iciythoueny: o?eieao, ui
aiaeiiaiaea? i?ioiiai o (-iieiaeaiii, ooe?aiee oa ciiuaiee o neeueia
iiea: ((H() = 2.69 i./. 2J(195Pt — H) = 85.9 Aoe; 3J(H — H) = 6.1 Aoe.
Aeacaii aiaeiiiiinoi II? — niaeo?ia iiaeooue aooe ianeiaeeii oaeaeeiai
?iaiiaaaeiiai ooai?aiiy o D2O iaoaeioeeeeo ca ?aooiie eii?aeeiaoei? c
ieaoeiith iai?ioiiiaaii? (-aiiiia?oie.

NOAAIEUeIINOUe (-AIIIIEAOEEUeIIAI EIIIEAENO IEAOEIE (IV)

Ciaiioiueinoa?iee ?iceeaae. Aaeaea ii?aeiaiiy aiaeiinii?
noaaieueiinoi c eaaeinoth ?iceeaaeo o aiaeieo ?ic/eiao c?iaeei
(-aeeieueii eiiieaene ieaoeie (IV) c?o/iith iiaeaeeth aeey aea/aiiy
iioe?aii? ?aaeoei? iaoaeii?aaii/ieo niieoe — aiaeiiaiiai aeiiiioaaiiy
(2).

?iceeaae ca noaiith (2) o eeneeo oei?eaeieo ?ic/eiao eiiieaeno (1a)
aiaeaoaa?oueny c ooai?aiiyi ?aeeii? i?aaii/ii? niieoee —
(-oei?aiiiiaoaio. Eiiaoeea oei?? ?aaeoei? i?e [Cl-] >> [RPt(IV)] oa
iinoieiie eiiiie neei [HCl] + [HClO4] = 3.0 M aiaeiiaiaea? ?iaiyiith
ia?oiai ii?yaeeo ii iaoaeii?aaii/iiio noano?aoo. Caeaaeiinoue eiinoaioe
oaeaeeinoi ?iceeaaeo eiiieaeno (1a) k = d(ln[RPt(IV)])/d( aiae [Cl-]
ia? aeaeyae e?eai? c iane/aiiyi (?en.1) oa aiaeiiaiaea? cae/aeiiio aeey
?aaeoei? (2) ?iaiyiith (3).

?en.1. Caeaaeiinoue eiinoaioe oaeaeeinoi k aiaeiiaiiai aeiiiioaaiiy
eiiieaeno (1a) aiae eiioeaio?aoei? Cl-, 361 K.

(3)

A oeueiio ?iaiyiii KCl — eiinoaioa ?iaiiaaae

a k1 — eiinoaioa oaeaeeinoi SN2-aoaee Cl- ia (-aoii aoaeaoeth o
eiiieaeni o?ain-RPtCl4(H2O). O eeneiio na?aaeiaeui (-aiiiieaoeeueiee
eiiieaen ieaoeie (IV) noaaieueiioee ca aiaeiieo aiaeiaia: ( —
aoeaoiiieueiiai oa iaoeeueiiai iioiaeieo ia aeaa oa o?e ii?yaeee
aiaeiiaiaeii. Aaee/eie KCl aeey aeacaieo iaoaeii?aaii/ieo niieoe iaeiiai
ii?yaeeo, ioaea aiaeiiiiinoue o noaaieueiinoi oeeo niieoe iia’ycaii
ci ciiiith aaee/eie k1. Ii?iaiyiiy aaee/ei aeoeaaoeieieo ia?aiao?ia c
aiaeiiaiaeieie /eiieeaie aeey iaoeeueiiai oa aoeaoiiieueiiai iioiaeieo
iieaco?, ui aia?ai? aeoeaaoei? ?aaeoei? (2) o iaaeao aenia?eiaioaeueieo
iiieeie caiaathoueny, a aiaeiiia o ?aaeoeieiie caeaoiinoi eiiieaenia
RPt(IV) a iineiaeiaiinoi R = CH3, CH2COCH3 oa CH2CH2NH3+ coiiaeaia
aiaeiiiiinoth i?aaeaeniiiaioeieieo iiiaeieeia, ui, iiaea aooe iiyniaii
?inoii noa?e/ieo oneeaaeiaiue aeey SN2- caiiuaiiy o aeacaiiio ?yaei.

Aioo?ioiueinoa?ia aiaeiiaia aeiiiioaaiiy. O eoaeieo ?ic/eiao i?e
aeai?ioiioaaiii aiiio iiyaa ioeeaioieueiiai oeaio?o aeeeeea? i?ioieaiiy
?iceeaaeo oeyoii aioo?ioiueiiieaeoey?io? ioeeaioieueii? aoaee aiiiia?oie
ia (-aoii aoaeaoeth o eiiieaeni o?ain- Pt(CH2CH2NH2)Cl4(H2O)-. Ia?ainii
i?iaeoeoe i?e oeueiio- ace?eaeei (Az) oa PtCl42-. Az eii?aeeio?oueny aei
iai?i?aaaiaaiiai eiiieaeno a o?ain-iieiaeaiiy uiaei i?aaii/iiai eiaaiaeo
c ooai?aiiyi iioiaeiiai, noieeiai aei aiaeiiaiiai eeiiiioaaiiy.
Oeeeeiiaoaethaaiiy o inoaiiueiio aea? eiiieaen Pt(CH2CH2NH2)(Az)Cl3 yeee
ia ia? ca?yaeo.

Oa?aeoa? II?-niaeo?o ?aaeoeieii? noiioi aea? ciiao eacaoe i?i
i?enooiinoue a iie i?e /anoeiaie iaeo?aeicaoei? (1a) e?ii eiiiiiaioia
(1a) oa (1b) /anoeiie, ui iathoue NH2CH2CH2 — (aai NH3CH2CH2- )
oa?oioaaiiy, iia’ycaii c ieaoeiith. A?aoiaoth/e oeae oaeo, eiiai?io
noaio ia?aoai?aiiy (1a) ( (1b) ( (1c) iiaeeeai oyaeoe o aeaeyaei
noeoiiinoi noaaeie:

Pt(CH2CH2NH2)Cl52- + H2O (5)

(1a)

o?ain-Pt(CH2CH2NH2)Cl4(H2O)-+Cl-, (6)

o?ain- Pt(CH2CH2NH2)Cl4(OH)2- + H2O , (7)

o?ain-Pt(CH2CH2NH2)Cl4((-NH2CH2CH2)PtCl4(H2O)2- + H2O, (8)

AzH+ + PtCl42- + H2O, (9)

Az + H2O ,
(10)

o?ain-Pt(CH2CH2NH2)Cl4Az-+H2O

(1b) (11)

(1c)

Iaoaeioeeee Pt(CH2CH2NH2)(Az)Cl3 aeaeieaii o aiaeioe/ii /enoiio noaii.

Iaea?aeaii: %: N 11.9; H 3.2; N 6.8; Pt 51.1.

?ic?aoiaaii aeey C4H11Cl3N2Pt , %: N 12.36; H 2.85; N 7.21; Pt 50.20.

A I*-niaeo?i i?iaeoeoo (oaa. c KBr, (, ni ) ?a?no?othoueny nioae 3269
n., 3190 ae.n. (NH), 3000 ae.ne., 2913 na?. 2844 ne. (CH), a oaeiae
nioae 1230 ae.n. oa 877 ae.n., eio?i aiaeiinyoue aei eieeaaiue
eii?aeeiiaaiiai aei ieaoeie (IV) ace?eaeeio. O eeneiio na?aaeiaeui
iaoaeioeeee ?iceeaaea?oueny c ooai?aiiyi i?ioiiiaaiiai ace?eaeeio (( =
2.71) oa ii/aoeiaiai eiiieaeno (1a) (((H()=3.95 (o), J(HH) = 5.82;
2J(195Pt — 1H) = 85.0. ((H() = 2.68 (o). Ca aeaiieie aoiiiiaiinieii?
niaeo?ineiii? eiiieaen (1N) ia iinoeoue o niai eaeith.

I?e iinoieiie eiioeaio?aoei? Cl- ( [Cl-] =3.0 M) oa O=30(N
caeaaeiinoue eiinoaioe oaeaeeinoi k = — (dlnD/d() aiae ?I na?aaeiaeua
ia? aeaeyae e?eai? oeo?oaaiiy. (Oaae.1). Oea aeiaiaeeoue, ui
(-aiiiieaoeeueiee eiiieaen ?aaao? o aeai?ioiiiaaiie oi?ii. Ioeiiaia c
eiiaoe/ieo aeaieo cia/aiiy pKa aeey ieaoeiiaiiiiaoaio (pKa ( 8.2)
aeecueea aei aiaeiiaiaeieo cia/aiue aeey (-a?ii oa (- ooi?aiiiiaoaio.

Oaaeeoey 1.

pH k ( 103, c-1

5.6 0.17(0.01

6.0 0.80(0.03

7.0 1.7(0.1

7.5 2.0(0.1

8.0 6.3(0.3

8.3 25.9(0.6

8.8 42.0(1.7

Caeaaeiinoue eiinoaioe oaeaeeinoi k

aiae pH na?aaeiaeua. [NaCl] = 3.0 M, 30( N.

Oaeei /eiii, (-aiiiieaoeeueiee eiiieaen ieaoeie (IV) caeaaeii aiae
oiia anooia? o aeaa oeio ia?aoai?aiue: aioo?ioiuei- oa ciaiioiueinoa?ia
aiaeiiaia aeiiiioaaiiy. O eeneeo ?ic/eiao, aea ?aaeico?oueny
ciaiioiueinoa?iee oeyo ?iceeaaeo, eiiieaen (1a) cia/ii noaaieueiioee ca
naie aiaeia: (-aoeaoiiieueiee eiiieaen ieaoeie (IV). O eoaeieo ?ic/eiao,
i?e aeai?ioiioaaiii aiiiieii? a?oie eiiieaen (1a) ?iceeaaea?oueny ca
aioo?ioiueinoa?iei iaoaiiciii. Ca oeeo oiia (1a) iaaaaaoi aeoeaiioee
(-aoeaoiiieueiiai iioiaeiiai, aeey yeiai oaea aeiiiioaaiiy iaiiaeeeaa.
A?aoiaoth/e, ui ciaiioiueinoa?ia ?aaeoeiy aiaeaoaa?oueny ca SN2 —
iaoaiiciii, iiaeia i?eionoeoe, ui aioo?ioiueinoa?ia aiaeiiaia
aeiiiioaaiiy ? oaeiae SN2 — i?ioeanii.

Aaaeeeaei aeniiaeii o?aaa aaaaeaoe oie oaeo, ui a iaio aeiaaeeao a
?aaeoeith anooiathoue eeoa oi eiiieaene, yei iathoue a
o?ain-iieiaeaiii uiaei i?aaii/iiai eiaaiaeo eii?aeeiaoeieio aaeainith
(oeyo a), aai iieaeoeo aiaee (oeyo a):

(13)

X = Cl-, Br-, I-, S2O32-, Am

Y = Cl-, Am.

Iaeaeaa ia?o?ooe eiiaoe/ii ia ?icaeieueii oa i?ecaiaeyoue aei ?iaiyiiy
(14):

(14)

EIIAOEEA OA IAOAIICI ?ICEEAAeO ( — AIIIIEAOEEUeIIAI EIIIEAENO
IEAOEIE(IV) O AIAeIEO EIAeEAeIEO ?IC*EIAO

Ie ciaeoee, ui i?e 80(N o nenoaii PtII (0.01-0.1 M) — NaI (5 M) —
Na2HPO4 (0.07 M) — KH2PO4 (0.07 M) — H2O eiiieaen (1a) ?iciaaea?oueny
c ooai?aiiyi aoeeaio. Aac aeiiioie ieaoeie (II) oey ?aaeoeiy c iiiioiith
oaeaeeinoth ia eaea. E?iaoe/ia e?eaa (?en.2) neeaaea?oueny c aeaio
/anoei: iae?aco i?ney ii/aoeo ?aaeoe?? oaeaeei ooai?th?oueny iaaaeeea
e?euee?noue aoeeaio, i?ney /iai niinoa??aa?oueny a?aeiinii iia?eueia
eiai iaeiie/aiiy. Aeey c’ynoaaiiy iaoai?cio ia?aoai?aiiy nooo?aei oaeoii
? oa, ui aeae?eaiiy aoeeaio a?aeaoaa?oueny oaeiae i?e aeiaeaaaii?a
?aaeoe?eio noi?o (-a?iiai?iiaoaio cai?noue eiiieaeno (1a). O
a?aenooiino? aeii?oie ieaoeie (II) inoaiiy ?aaeoe?y ia eaea. Oaeaee?noue
aeae?eaiiy aoeeaio i?e noa?o? c (-a?iiai?iiaoaio aeecueea aei oaeaeeino?
eiai a?aeoai?aiiy c eiiieaeno (1a) i?e iaeiaeiaeo ii/aoeiaeo
eiioeaio?aoe?yo (1a) oa BrCH2CH2NH3+.

?en.2. Oeiiaa

e?iaoeea aeae?eaiiy

aoeeaio a ?aaeoe??

eiiieaena (1a):

[K2PtCl4] = 0.1 M;

[K2PtCl6] = 0 M;

[PtIVCH2CH2NH3+] =

0.001 M;

Iacaeaaeii, caniaii II?-niaeo?ineii?? iieacaii, ui aaea i?e 20(N
eiiieaen (1a) o aiaeiiio (D2O) eiaeeaeiiio ?ic/ei? ([NaI] = 5.0 M)
oaeaeei ?iceeaaea?oueny c ooai?aiiyi (-eiaeai?iiaoaio (aeaa o?eieaoe c (
= 3.98 oa 2.69 i./.; JHH = 5.4 Aoe). Oe? aeaii? aeathoue ciiao
i?eionoeoe, ui iae?aco i?ney aeiaeaaaiiy eiiieaeno (1a) a ?aaeoe?eio
noi?o iathoue i?noea aea? ia?aeaeuei? ?aaeoe??: /anoeiai eiiieaen
ooai?th? aoeeai, aea cia/iith /anoeiith eaea ?iceeaae (1a) aiane?aeie
a?aeiiaiiai ae?i?ioaaiiy i?ae ae??th eiaeeae-eii?a aei iaaaeeei?
noaoe?iia?ii? eiioeaio?aoe??. E?iaoeea ?aaeoe?? iaaiai?th?oueny naia
aeey noaoe?iia?iiai ?aaeeio. O aeiaaeeo, eiee a ?aaeoe?eiee ?ic/ei
aeiaea?oueny cai?noue eiiieaeno (1a) (-a?iiai?iiaoai, inoaii?e iiaeiai
oaeaeei ia?aoai?thaaoenue aiane?aeie SN2 — cai?uaiiy a (-eiaeai?iiaoai,
yeee aeae? aea? ( — aiii?eaoeeueiee eiiieaen ieaoeie (1a). Oeei
iiynith?oueny aeecuee? ii/aoeia? oaeaeeino? ooai?aiiy aoeeaio i?e noa?o?
c (1a) oa (-a?iiai?iiaoaio.

I?e iino?ei?e eiioeaio?aoe?? ieaoeie (II) oaeaee?noue aeae?eaiiy
aoeeaio e?i?eii caeaaeeoue a?ae aeo?aeii? eiioeaio?aoe?? eiiieaeno (1a).
A?aeiia?aei? eiinoaioe iaaaaeai? o oaae. 2. Cia/aiiy k ca?eueoothoueny c
?inoii eiioeaio?aoe?? ieaoeie (II), i?e/iio caeaaei?noue aeecueea aei
eaaae?aoe/ii?. Aeii?oee ieaoeie (IV) cia/ii cieaeothoue oaeaee?noue
iaeiie/aiiy aoeeaio.

Oaaeeoey 2.

Caeaaeiinoue eiinoaioe oaeaeeinoi ia?oiai ii?yaeeo iaeiie/aiiy

aoeeaio i?e ?iceeaaei eiiieaeno K[Pt(CH2CH2NH3)Cl5] aiae

eiioeaio?aoei? K2PtCl4 oa K2PtCl6; [NaI] = 5.0 M; 80(N; pH = 7.0.

[K2PtCl4], M [K2PtCl6], M k ( 106, c-1

0 0 < 0.01 0.011 0 1.20(0.04 0.03 0 6.4(0.4 0.05 0 12.9(0.3 0.075 0 26.7(0.8 0.1 0 36.8(2.3 0.1 0.001 3.6(0.03 0.1 0.005 0.7(0.02 0.1 0.0075 0.52(0.02 0.1 0.01 0.4(0.02 Iaaaaeaii o ?iaioi ?acoeueoaoe ocaiaeaeothony ci noaiith (15), ui aeeth/a? e?ii noaaei? (1) iai?ioia eiiieaiaioa?ia aiaeiiaeaiiy (noaaeiy 2) (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV) aei aiaeiiaiaeiiai iioiaeiiai ieaoeie (II) i ?iceeaae PtII(CH2CH2NH3) c aeaeieaiiyi C2H4 (noaaeiy 3): Caaaeaia noaia ca oiiaaie noaoeiiia?iinoi uiaei ieaoeiii?aaii/ieo iioa?iaaeiaoia i?eaiaeeoue aei ?iaiyiiy (ki - eiinoaioe oaeaeeinoi aiaeiiaiaeieo noaaeie ca noaiith 15): yea i?e iinoieiiio cia/aiii [H+] (oinoaoiee aooa?) ai?ii ia?aaea? caeaaeiinoue k aiae eiioeaio?aoei? ieaoeie (II) oa ieaoeie (IV). Eiiieii aiaii?oice (?en.3) caaaeaieo caeaaeiinoae aeathoue ciiao aeyaeoe cia/aiiy ia?aiao?ia k1 = (5.6(0.5)(10-4 e/iieue (n, oa K1K2k3 = (4.0(0.2) (10-7 iieue/e, aea K1 = k1/k-1 oa K2 = k2/k-2 - eiinoaioe ?iaiiaaae aiaeiiaiaeieo noaaeie. Aiaecia/eii, ui aeaeieaiiy aoeeaio i?e ?iceeaaei (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV) niinoa?iaa?oueny oieueee iiney aiaeiiaeaiiy inoaiueiai aei aiaeiiaiaeiiai iioiaeiiai ieaoeie (II). I?e?iaeia iiyniaiiy oeueiai oaeoo - noaaieicaoeiy aoeeaio, ui aeaeiey?oueny ca ?aooiie (-eiiieaeniooai?aiiy c iioiaeiei ieaoeie (II). ?en.3. Caeaaeiinoue eiinoaioe oaeaeeinoi ia?oiai ii?yaeeo k aeaeieaiiy aoeeaio aiae eiioeaio?aoei? ieaoeie (II). Aiaii?oica ?iaiyiiy (16). AENIIAEE 1. Ciaeaeaii iiao ?aaeoeith oei?eaeieo eiiieaenia ieaoeie (II) c ace?eaeeiii o eeneeo aiaeieo ?ic/eiao. Aeiaaaeaii, ui ieaoeia (II) a oeeo oiiaao ?ice?eaa? ace?eaeeiiaee oeeee c ooai?aiiyi eiiieaeno ieneaeaoeaiiai i?e?aeiaiiy, yeee ia? (-ca’ycie ieaoeia-aoaeaoeue ia aiaeiiio aiae aiaeiieo ?aaeoeie aoeeaiiiiio ci caaaeaieie eiiieaenaie a iaeo?aeueieo aiaeieo ?ic/eiao. 2. Oeyoii ieneaeaoeaiiai i?e?aeiaiiy ace?eaeeio aei ieaoeie (II) a eeneeo aiaeieo ?ic/eiao neioaciaaii iaaeinooiiee ?aiioa (-aiiiieaoeeueiee eiiieaen ieaoeie (IV)- KPtCl5(CH2CH2NH3). 3. Iieacaii, ui eiiaoeea ieneaeaoeaiiai i?e?aeiaiiy aoeeaiiiiio aei oei?eaeieo eiiieaenia ieaoeie (II) aiaeiiaiaea? SN2 -iaoaiicio, ui aeeth/a? ioeeaioieueio aoaeo aeiaiiiio PtCl42- ia aoii aoaeaoeth i?ioiiiaaiiai ace?eaeeio. Aecia/aii aeoeaaoeieii ia?aiao?e oei?? ?aaeoei?. Iieacaii, ui aeaaoei?eaeii eiiieaene ieaoeie (II) c iiiioiith oaeaeeinoueth ia ?aaaothoue. 4. Aeineiaeaeaia noaaieueiinoue (-aiiiieaoeeoei?eaeiiai eiiieaeno ieaoeie (IV) uiaei aiaeiiaiiai aeiiiioaaiiy iiae aei?th Cl- a eeneeo aiaeieo ?ic/eiao. Iieacaii, ui iaoaiici oei?? ?aaeoei? aeeth/a? SN2 -aoaeo Cl- ia (-aoii aoaeaoeth a eiiieaeni Pt(CH2CH2NH3+)Cl4(H2O), o oie /an ye eiiieaen [Pt(CH2CH2NH3+)Cl5]- ia ?aaao?. Aecia/aii aeoeaaoeieii ia?aiao?e aeacaii? ?aaeoei? . 5. Aeyaeaii oa aeineiaeaeaii ?aaeoeith aioo?ioiueinoa?iiai aeiiiioaaiiy a neioaciaaiiio (-aiiiieaoeeueiiio eiiieaeni. ?aaeoeiy iiiiiieaeoey?ia e aeeth/a? ioeeaioieueio aoaeo aieueii? aiiiia?oie ia iia’ycaiee c ieaoeiith (-aoii aoaeaoeth c ianooiiith oeeeeicaoei?th (-iaoaeieiiieaeniiai iioiaeiiai aiiiiaoaio a aoeeaiiiii. Aeaii ioeiieo pKa aiaeiiaiaeiiai (-iaoaeieiiieaeniiai iioiaeiiai aiiiiaoaio. 6. Iieacaii, ui aioo?ioiueinoa?ia aeiiiioaaiiy, oaeiae ye cia- iioiueinoa?ia, aaeueio?oueny aiiiaie (ace?eaeei, iiiaeacie) ca ?aooiie eii?aeeiaoei? inoaiiio aei aoiio acioo a o?ain-iieiaeaiiy aiaeiinii ae- eieueiiai eiaaiaeo. 7. Neioaciaaii iaoaeioeeee PtCl3CH2CH2NH2(Az) - eiioeaaee i?iaeoeo ?iceeaaeo aiiiiaoeeueiiai eiiieaeno ieaoeie (IV). 8. Aeyaeaii iiao ?aaeoeith ?iceeaaeo (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV) o aiaeieo eiaeeaeieo ?ic/eiao c ooai?aiiyi aoeeaio. Aeineiaeaeaii noaaeieiee iaoaiici ?aaeoei?. Anoaiiaeaii, ui aeaeieaiiy aoeeaio i?ioiea? /a?ac eiiieaiaioa?ia aiaeiiaeaiiy (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV) aei aiaeiiaiaeiiai iioiaeiiai ieaoeie (II). INIIAIEE CIINO AeENA?OAOeI? AEEEAAeAII O ?IAIOAO: 1. Ieo/aiei N.A., Caiaueeia A.A., Neeieei N.I., Aiuoea A.I. ?ane?uoea aoeeaeieiiieaenaie ieaoeiu (II) ace?eaeeiiaiai oeeeea. Neioac eiiieaena K[Pt(CH2CH2NH3)Cl5]. // AEo?i. iauae oei.- 1991.- o.61.- ? 9.- n. 2127-2128. 2. Ieo/aiei N.A., Neeieei N.I., Aaeiae/aiei A.I., Caiaueeia A.A. Ieeneeoaeueiia i?eniaaeeiaiea yoeeaieieia e oei?eaeiui eiiieaenai ieaoeiu (II) a aiaeiuo ?anoai?ao // Iaoaeeii?aaie/aneay oeiey.- 1991.- o.4. - ? 5.- n.1031-1035. 3. Ieo/aiei N.A, Caiaueeia A.A, Neeieei N.I. Aioo?eiieaeoey?iia ainnoaiiaeoaeueiia yeeieie?iaaiea i?e ?aniaaea (-aiiiieeyoeeueiiai eiiieaena ieaoeiu (IV) a aiaeiuo uaei/iuo ?anoai?ao. // AEo?iae iauae oeiee.- 1993.- o.63.- aui.4.- n.956-957. 4. Caiaueeia A.A, Ieo/aiei N.A., Neeieei N.I. Aioo?e- e aiaoia-noa?iia ainnoaiiaeoaeueiia yeeieie?iaaiea i?e ?aniaaea (- aiiiieeyoeeueiiai eiiieaena ieaoeiu (IV) a aiaeiuo ?anoai?ao // Ecaanoey AI.- Na?.oei.- 1994.- ? 3.- n.518-523. 5. Caiaueeia A.A., Neeieei N.I., Aecaa?o ?.A. Iiaue iooue ?aniaaea (-aiiiieeyoeeueiiai eiiieaena ieaoeiu (IV); Yeeieie?iaaiea (- aiiiieeiie a?oiiu. // Eca.A.I., Na?.oei.- 1996.- ? 7.- n.1869. 6. Ieo/aiei N.A., Caiaueeia A.A., Neeieei N.I., Aecaa?o ?.A. Eeiaoeea e iaoaieci ?aniaaea (-aiiiieeyoeeueiiai eiiieaena Pt(IV) a aiaeiuo eiaeeaeiuo ?anoai?ao // Eeiaoeea e eaoaeec.- 1997.- o.38.- n. 667-670. AIIOAOe?ss Neiieii N.I. Neioac oa ?aaeoeieia caeaoiinoue (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV).-?oeiien. Aeena?oaoeiy ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa oiii/ieo iaoe ca niaoeiaeueiinoth 02.00.03- i?aaii/ia oiiiy.-Aeiiaoeueeee aea?aeaaiee oaoii/iee oiiaa?neoao, Aeiiaoeuee, 1998. Aeena?oaoeith i?enay/aii oiii? aoeeaeieiiieaenia ieaoeie. Ciaeaeaii iiaee eean ?aaaaioia a ?aaeoeiyo aeeiethaaiiy eiiieaenia ieaoeie (II). Aecia/aii oiiae ieneaeaoeaiiai i?e?aeiaiiy aei aoeeaeieiiieaenia ieaoeie (II) ace?eaeeio. Aeiaaaeaii, ui ?aaeoeiy aiaeaoaa?oueny ca SN2 - iaoaiiciii, aeoeaiith ioeeaioieueiith /anoeith ? PtCl42-. Iaiaoiaeia oiiaa - iiia?aaei? i?ioiioaaiiy ace?eaeeio. Aeineiaeaeaii noaaieueiinoue iioiaeieo i?e?aeiaiiy a ?aaeoei? ciaiioiueinoa?iiai aeiiiioaaiiy. Ciaeaeaii oa aeineiaeaeaii iiao ?aaeoeith aioo?ioiueinoa?ii? oeeeeicaoei? iaea?aeaiiai iioiaeiiai iiae aei?th eoaia. Ciaeaeaii iiao ?aaeoeith ?iceeaaeo (-aiiiieaoeeueiiai eiiieaeno ieaoeie (IV) o aiaeieo eiaeeaeieo ?ic/eiao c ooai?aiiyi aoeeaio. Aeiaaaeaii, ui aeaeieaiith aoeeaio iiia?aaeaea? eiiieaiaioa?ia aiaeiiaeaiiy eiiieaeno ieaoeie (IV) aei aiaeiiaiaeiiai iioiaeiiai ieaoeie (II). Eeth/ia? neiaa: ieaoeia, aoeeaeieiiieaene, ieneaeaoeaia i?e?aeiaiiy, a?aeiiaia ae?i?ioaaiiy, aaoa?ioeeee?caoe?y, ace?eaeei. AIIIOAOeEss Neeieei N.I. Neioac e ?aaeoeeiiiay niiniaiinoue (- aiiiieeyoeeueiiai eiiieaena ieaoeiu (IV). - ?oeiienue. Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe ii niaoeeaeueiinoe 02.00.03- i?aaie/aneay oeiey.- Aeiiaoeeee ainoaea?noaaiiue oaoie/aneee oieaa?neoao, Aeiiaoee 1998. Aeenna?oaoeey iinayuaia oeiee aoeeaeieiiieaenia ieaoeiu. Iaia?oaeai iiaue eeann ?aaaaioia a ?aaeoeeyo aeeeee?iaaiey eiiieaenia ieaoeiu (II). Ii?aaeaeaiu oneiaey ieeneeoaeueiiai i?eniaaeeiaiey e aoeeaeieiiieaenai Pt(II) ace?eaeeia. Onoaiiaeaii, /oi ?aaeoeey i?ioaeaao ii SN2 - iaoaiecio, aeoeaiie ioeeaioeeueiie /anoeoeae yaeyaony PtCl42-. Iaiaoiaeeiui oneiaeai yaeyaony i?aaeaa?eoaeueiia i?ioiie?iaaiea ace?eaeeia. Enneaaeiaaia noaaeeueiinoue i?iaeoeoia i?eniaaeeiaiey a ?aaeoeee aiaoianoa?iiai ainnoaiiaeoaeueiiai yeeieie?iaaiey. Iaia?oaeaia e enneaaeiaaia iao?eaeaeueiay ?aaeoeey aioo?enoa?iie oeeeeecaoeee iieo/aiiiai i?iecaiaeiiai iiae aeaenoaeai iniiaaiee. Iaia?oaeaia iiaay ?aaeoeey ?aniaaea (-aiiiieeyoeeueiiai eiiieaena ieaoeiu (IV) a aiaeiuo eiaeeaeiuo ?anoai?ao n auaeaeaieai yoeeaia. Onoaiiaeaii, /oi auaeaeaieth yoeeaia i?aaeoanoaoao eiiieaiaioa?iia ainnoaiiaeaiea eiiieaena ieaoeiu (IV) aei niioaaonoaothuaai i?iecaiaeiiai Pt (II). Eeth/aaua neiaa: ieaoeia, aoeeaeieiiieaenu, ieeneeoaeueiia i?eniaaeeiaiea, ainnoaiiaeoaeueiia yeeieie?iaaiea, aaoa?ioeeeeecaoeey, ace?eaeei. ABSTRACT Slinkin S.M. Synthesis and reactivity of platinum (IV) b-ammonium ethyl complex.- Manuscript. Thesis, Candidate of Sciences (Chemistry), Speciality- Organic Chemistry. Donetsk State Technical University, Donetsk, 1998. A new class of reagents for platinum (II) complexes alkylation has been found. The conditions of aziridine oxidative addition to Pt(II) acido complexes has been determined. The reaction proceeds through SN2 mechanism, the active complex is PtCl42-. The necessary condition for the reactions is the previous aziridine protonation. The resulting product stability toward the inter sphere reductive elimination has been investigated. The intra sphere cyclization of the complex obtained under the alkaline action has been found. A new route for decomposition of the platinum (IV) (-ammonioethyl complex in aqueous iodide solution yielding ethylene has been established. It has been shown that the complementary reduction of the platinum (IV) (-ammonioethyl complex to the corresponding derivative of platinum (II) precedes the ethylene formation. The key words: platinum, acidocomplexes, oxidative addition, reductive elimination, heterocyclization, aziridine. PAGE 4 PAGE 3 ], M II [Pt c 2 M / k, 2 ] II [Pt 250 200 150 100 0,10 0,08 0,06 0,04 0,02 0,00 - H (15) . 5 + + 4 H N 3 H N + H 3 4 + H 3 N 2 H C C 2 H + + + I I t P I I t P 3 H N 2 H C 3 H C + 2 -2 V I t P I I t P 3 H N 2 H C 2 H C + I I t P - 1, -I -1, I I I t P + + + 3 H N 2 H C 2 H C I 3 H N 2 H C 2 H C V I t P , . M 6 ](10 4 H 2 [C 60 40 20 30 20 10 0 l (12) - - N ) 2 H N 2 H C 2 H C ( t P z A 3 l C C - ) 2 H 2 H C 2 H C ( t P + z A 4 l C O, (4) + 2 H - 5 l C t P R - Cl ) O 2 H ( 4 l C t P R ], M - [Cl -1 , c 4 k(10 8 6 4 2 0 3,0 2,5 2,0 1,5 1,0 0,5 0,0 H . (2) + 3 N 2 H C 2 H C l C + + - 2 4 l C t P l C K + - l C + ) 3 H N 2 H C 2 H C ( 5 l C t P K

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