A dynamic nuclear magnetic resonance study of 1,3-intramolecular shifts in pentacarbonyl-chromium(O) and -tungsten(O) complexes of β-2,4,6-trimethyl-1,3,5-trithian, 1,3,5-trithian, 1,3-dithian and 2-methyl-1,3-dithian: the x-ray crystal structure of [W(CO)<sub>5</sub>{SCH(Me)SCH(Me)SCH(Me)}]期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

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A dynamic nuclear magnetic resonance study of 1,3-intramolecular shifts in pentacarbonyl-chromium(O) and -tungsten(O) complexes of β-2,4,6-trimethyl-1,3,5-trithian, 1,3,5-trithian, 1,3-dithian and 2-methyl-1,3-dithian: the x-ray crystal structure of [W(CO)₅{SCH(Me)SCH(Me)SCH(Me)}]

Authors:	Edward W Abel Gary D King Keith G Orrell Graham M Pring Vladimir Sik TStanley Cameron

Institution:	Department of Chemistry, University of Exeter, Exeter EX4 4QD, England;Chemistry Department, Dalhousie University, Halifax, Nova Scotia, Canada B3H 3JB

Abstract:	Variable temperature ¹H NMR spectroscopy has been used in the study of 1,3-intramolecular shifts of the M(CO)₅ moiety in complexes of the general formula M(CO)₅L], (M = Cr or w), L = $SCH_{2} SCH_{2} SC$ H₂, $SCH_{2} SCH_{2} CH_{2} C$ H₂ and $SCH(Me)SCH_{2} CH_{2} C$ H₂. For the 1,3,5-trithian complexes precise energy barriers for the process have been obtained by detailed computer simulation of the static and dynamic spectra. Our results suggest that the magnitude of ΔG^≠ (298.15 K) for the 1,3-shift is largely dependent upon the skeletal flexibility of the ligand system. In this context we have investigated the X-ray crystal structure of the highly substituted trithian complex W(CO)₅{β- $SCH(Me)SCH(Me)SC$ H(Me)}].

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