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

来源：

ORGANOMETALLICS | 1991年 / 10卷 / 01期

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

页码：49 / 52

页数：4

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].