ALKYL(HYDRIDO)PIATINUM(IV) COMPLEXES - THE MECHANISM OF PT-C BOND PROTONOLYSIS

被引：137

作者：

HILL, GS ^{[1
]}

RENDINA, LM ^{[1
]}

PUDDEPHATT, RJ ^{[1
]}

机构：

[1] UNIV WESTERN ONTARIO,DEPT CHEM,LONDON,ON N6A 5B7,CANADA

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 10期

关键词：

D O I：

10.1021/om00010a073

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complexes [PtMe(2)(N-N)] {N-N = (t)bu(2)-bpy (4,4'-di-tert-butyl-2,2'-bipyridine), bpy (2,2'-bipyridine), or phen (1,10-phenanthroline)} react with HX(X = Cl, Br, I, O2CCF3, SO3CF3) to yield [PtXMe(N-N)] and CH4, by an oxidative addition/reductive elimination mechanism. The new alkyl(hydrido)platinum(IV) intermediates [PtCl(H)Me(2)((t)bu(2)bpy)])] (1), [PtBr(H)Me(2)((t)bu(2)bpy)] (2), [PtH(I)Me(2)((t)bu(2)bpy)] (3), and [Pt(Cl(H)Me(2)(bpy)], (4), formed by trans oxidative addition of HX; have been fully characterized at -78 degrees C by H-1 NMR spectroscopy. Rapid reductive elimination of CH4 ensues at higher temperatures to yield the corresponding organoplatinum(II) products [PtXMe(N-N)]; The thermal stability of the platinum(IV) intermediates follows the sequence X = Cl > Br > I > O2CCF3, SO3CF3.

引用

页码：4966 / 4968

页数：3

共 32 条

[1] ORGANOPLATINUM(IV) POLYMERS AND MODEL COMPLEXES BY OXIDATIVE ADDITION OF BROMOACETATE ESTERS [J].

ACHAR, S ;

SCOTT, JD ;

VITTAL, JJ ;

PUDDEPHATT, RJ .

ORGANOMETALLICS, 1993, 12 (11) :4592-4598

[2] 5-COORDINATE ALKENE COMPLEXES OF PALLADIUM(II) AND PLATINUM(II) [J].

ALBANO, VG ;

NATILE, G ;

PANUNZI, A .

COORDINATION CHEMISTRY REVIEWS, 1994, 133 :67-114

[3] ROLE OF HALIDE ION IN THE MECHANISM OF PROTONOLYSIS OF THE PT-C BOND IN PT(II) ALKYL AND ARYL COMPLEXES [J].

ALIBRANDI, G ;

MINNITI, D ;

ROMEO, R ;

UGUAGLIATI, P ;

CALLIGARO, L ;

BELLUCO, U ;

CROCIANI, B .

INORGANICA CHIMICA ACTA-ARTICLES AND LETTERS, 1985, 100 (01) :107-113

[4] MECHANISM OF ELECTROPHILIC CLEAVAGE OF THE PT-C BOND IN TRANS-[PTX(CH2CME3)(PET3)2] BY HX (X=CL,BR) [J].

ALIBRANDI, G ;

MINNITI, D ;

ROMEO, R ;

UGUAGLIATI, P ;

CALLIGARO, L ;

BELLUCO, U .

INORGANICA CHIMICA ACTA, 1986, 112 (02) :L15-L16

[5] COMPETITION BETWEEN INTRAMOLECULAR OXIDATIVE ADDITION AND ORTHO METALATION IN ORGANOPLATINUM(II) COMPOUNDS - ACTIVATION OF ARYL HALOGEN BONDS [J].

ANDERSON, CM ;

CRESPO, M ;

JENNINGS, MC ;

LOUGH, AJ ;

FERGUSON, G ;

PUDDEPHATT, RJ .

ORGANOMETALLICS, 1991, 10 (08) :2672-2679

[6] TRANS-INFLUENCE - ITS MEASUREMENT AND SIGNIFICANCE [J].

APPLETON, TG ;

CLARK, HC ;

MANZER, LE .

COORDINATION CHEMISTRY REVIEWS, 1973, 10 (3-4) :335-422

[7] ELECTROPHILIC ATTACK UPON TRANS-BIS(TRIETHYLPHOSPHINE)DIPHENYLPLATINUM [J].

BELLUCO, U ;

CROATTO, U ;

UGUAGLIA.P ;

PIETROPA.R .

INORGANIC CHEMISTRY, 1967, 6 (04) :718-&

[8] MECHANISMS OF NUCLEOPHILIC AND ELECTROPHILIC ATTACK ON CARBON BONDED PALLADIUM(II) AND PLATINUM(II) COMPLEXES [J].

BELLUCO, U ;

MICHELIN, RA ;

UGUAGLIATI, P .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 250 (01) :565-587

[9] MECHANISM OF ELECTROPHILIC REACTIONS OF CARBON-METAL BONDED PLATINUM(2) COMPLEXES . A COMPARISON BETWEEN TRANSITION AND POST-TRANSITION ORGANOMETALLIC COMPOUNDS [J].

BELLUCO, U ;

GIUSTINI.M ;

GRAZIANI, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (25) :6494-&

[10] SILYL AND GERMYL COMPOUNDS OF PLATINUM AND PALLADIUM .1. PLATINUM DERIVATIVES OF MONOSILANE AND MONOGERMANE [J].

BENTHAM, JE ;

CRADOCK, S ;

EBSWORTH, EA .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1971, (04) :587-&

← 1 2 3 4 →