AN NMR-STUDY OF THE FLUXIONALITY OF GROUP-VI METAL PENTACARBONYL COMPLEXES OF 1,3-DITHIOLANES

被引：4

作者：

ABEL, EW ^{[1
]}

ORRELL, KG ^{[1
]}

QURESHI, KB ^{[1
]}

SIK, V ^{[1
]}

机构：

[1] UNIV EXETER,DEPT CHEM,EXETER EX4 4QD,DEVON,ENGLAND

来源：

POLYHEDRON | 1990年 / 9卷 / 05期

关键词：

D O I：

10.1016/S0277-5387(00)80279-X

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complexes [M(CO)5(SC2H4SCRR′)] (M = Cr, Mo or W, R = R′= H; M = Cr or W, R = R′= Me, R = H, R′= Me, But or Ph) have been synthesized and characterized. Their solution stereodynamics were examined by 1H NMR spectroscopy. Pyramidal inversion of the metal-coordinated sulphur atoms occurs rapidly at ambient temperatures (ΔG‡ (298 K) = 40-44 kJ mol-1). An appreciably slower 1,3-metal-sulphur shift is also evident at temperatures where sulphur inversion is rapid on the proton NMR timescale. For the ligand complexes (R = R′ = H, Me) this shift is purely intramolecular in nature (ΔG† (298 K) values ∼ 78 kJ mol-1), in contrast to the 2-mono-substituted ligand complexes (R = H, R′ = Me, But, Ph) where it is accompanied by a dissociation process. © 1990.

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页码：703 / 711

页数：9

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