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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

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