Chiral ruthenium complexes with sulfur ligands;: X-ray structure of (R)Ru-Ru(NmCp)(CO)(PPh3)SCN (NmCp = neomenthylcyclopentadienyl)

被引：7

作者：

Tabatabaeian, K ^{[1
]}

Adams, H ^{[1
]}

Mann, BE ^{[1
]}

White, C ^{[1
]}

机构：

[1] Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2003年 / 688卷 / 1-2期

基金：

英国工程与自然科学研究理事会;

关键词：

sulfide epimerisation; thiocyanate; ruthenium; stereochemistry;

D O I：

10.1016/j.jorganchem.2003.08.034

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of Ru(NmCp)(CO)(PPh3)I (NmCp = neomenthylcyclopenta-dienyl) with AgSCN occurs with retention of configuration at the ruthenium to give the S-bonded Ru(NmCp)(CO)(PPh3)SCN. This was confirmed by determining the X-ray structure of (R)(Ru)-Ru(NmCp)(CO)(PPh3)SCN. The reaction of (S)(Ru)-Ru(NmCp)(CO)(PPh3)I with AgBF4 in CH2Cl2 followed by treatment with MeSR gave the following sulfide complexes [(RS)(Ru)-Ru(NmCp)(CO)(PPh3){S(Me)R}]BF4 (R = CH2Ph, Ph and Bu-t). NMR studies have shown that for R = CH2Ph the chiral sulfur centre binds to the chiral ruthenium centre with a 33% d.e. and the free energy for inversion of the S-centre is 49 +/- 1 kJ mol(-1). In contrast, with the bulky phenyl and tert-butyl substituents the chiral ruthenium centre shows an overwhelming preference (greater than or equal to 99%) for binding to one enantiomer of the sulfide ligand. Despite this, arguments are presented to show that this ruthenium system is not a suitable chiral auxiliary for use in synthesizing chiral sulfoxides from complexed sulphides. (C) 2003 Elsevier B.V. All rights reserved.

引用

页码：75 / 81

页数：7

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