New reactions and new products derived from α-deprotonated Fischer-type carbene complexes

被引：7
|
作者：
Cronje, S [1 ]
Julius, GR [1 ]
Stander, E [1 ]
Esterhuysen, C [1 ]
Raubenheimer, HG [1 ]
机构：
[1] Univ Stellenbosch, Dept Chem & Polymer Sci, ZA-7602 Stellenbosch, South Africa
来源：
INORGANICA CHIMICA ACTA | 2005年 / 358卷 / 05期
关键词：
aminocarbene complexes; four-membered chelates; cyclisation; carbene-thioether complex; carbene-phosphine complex; tungsten and chromium carbonyl compounds;
D O I：
10.1016/j.ica.2004.10.012
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Anionic Fischer-type aminocarbene complexes, [(CO)(5)M=C(NMe2)CH2]Li (M = Cr or W) react with Ph2PCl and [(Me-2(MeS)S][BF4] - a source of SMe+ - to afford acyclic complexes (CO)(5)M=C(NMe2)CH2X (X = PPh2, SMe2) and (CO)(5)M=C(NMe2)CHX2 X = SMe), the chelates (CO)(4)M=C(NMe2)CHXX (X = SMe) and (CO)(4)M=C(NMe2)CH2X (X=PPh2, SMe), and the bridged compounds (CO)(5)M=C(NMe2)CH2XM(CO)(5) (X = PPh2, SMe). Cyclisation occurs much faster for Cr than for W. Crystal structures illustrate the bonding behaviour in the new complexes and especially characterise carbene-phosphine and carbene-thioether four-membered chelates for the first time. The sulfur-donor in the tetracarbonyl complexes (CO)(4)Cr=C(NMe2)CH (SMe)SMe, and (CO)(4)Cr=C(NMe2)CH2SMe shows an exceptionally weak trans influence. (c) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码：1581 / 1594
页数：14
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