CONTROL OF INTRAMOLECULAR BETA-HYDROGEN MIGRATION IN COORDINATIVELY UNSATURATED (DIPHOSPHINE)PLATINUM ETHYL CATIONS

被引:97
作者
MOLE, L
SPENCER, JL
CARR, N
ORPEN, AG
机构
[1] UNIV SALFORD, DEPT CHEM & APPL CHEM, SALFORD M5 4WT, LANCS, ENGLAND
[2] UNIV BRISTOL, DEPT INORGAN CHEM, BRISTOL BS8 1TS, AVON, ENGLAND
关键词
D O I
10.1021/om00047a026
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Protonation of the complex [Pt(C2H5)2(P-segment-P)] or [Pt(eta-2-C2H4)(P-segment-P)] (P P = Bu(t)2P(CH2)nPBu(t)2(n = 2, 3) and o-(Bu(t)2PCH2)2C6H4) affords a series of cations characterized as either ethene-hydride or agostic ethyl complexes [Pt(H)(eta-2-C2H4)(P-segment-P)]+ or [Pt(C2H5)(P-segment-P)]+ by NMR spectroscopy and, in the case of [Pt(C2H5){Bu(t)2P-(CH2)3PBu(t)2)][CB11H12], by single-crystal X-ray diffraction. The size of the chelating diphosphine ligand is shown to control the extent of transfer of a hydrogen atom from the beta-carbon of the coordinated ethyl group to platinum with the smaller diphosphines favoring transfer to the metal. All the complexes show remarkably low barriers to intramolecular rearrangement.
引用
收藏
页码:49 / 52
页数:4
相关论文
共 8 条
[1]   DYNAMICS OF AGOSTIC COMPLEXES OF THE TYPE C5R5(C2H4)M(CH2CH2-MU-H)+ - ENERGY DIFFERENCES BETWEEN AND ANCILLARY LIGAND CONTROL OF AGOSTIC AND TERMINAL HYDRIDE STRUCTURES [J].
BROOKHART, M ;
LINCOLN, DM ;
BENNETT, MA ;
PELLING, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (07) :2691-2694
[2]  
BROOKHART M, 1988, PROG INORG CHEM, V36, P1
[3]   COORDINATIVELY UNSATURATED DIPHOSPHINE PLATINUM(II) ALKYL CATIONS - A NEW CLASS OF BETA-AGONISTIC COMPLEXES [J].
CARR, N ;
DUNNE, BJ ;
ORPEN, AG ;
SPENCER, JL .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (14) :926-928
[4]   THE SYNTHESIS AND STRUCTURE OF [CO(ETA-C5ME5)ET(P(PARA-TOLYL)3)] CATION - A MODEL FOR THE BETA-ELIMINATION TRANSITION-STATE [J].
CRACKNELL, RB ;
ORPEN, AG ;
SPENCER, JL .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (06) :326-328
[5]   IS A 16-ELECTRON, SIGMA-ETHYL INTERMEDIATE NECESSARY FOR HYDROGEN SCRAMBLING IN ETHYLENE HYDRIDE COMPLEXES [J].
GREEN, MLH ;
WONG, LL .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (10) :677-679
[7]   IMPLICATIONS OF 3-CENTER, 2-ELECTRON M-H-C BONDING FOR RELATED ALKYL MIGRATION REACTIONS - DESIGN AND STUDY OF AN ETHYLENE POLYMERIZATION CATALYST [J].
SCHMIDT, GF ;
BROOKHART, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (05) :1443-1444
[8]   OLEFIN INSERTION REACTION [J].
THORN, DL ;
HOFFMANN, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (07) :2079-2090