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

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• 作者：Cronje ; Stephanie ; Julius ; Gerrit R. ; Stander ; Elzet ; Esterhuysen ; Catharine ; Raubenheimer ; Helgard G.
• 关键词：Aminocarbene complexes ; Four-membered chelates ; Cyclisation ; Carbene??????thioether complex ; Carbene??????phosphine complex ; Tungsten and chromium carbonyl compounds
• 刊名：Inorganica Chimica Acta
• 出版年：2005
• 出版时间：March 15, 2005
• 年：2005
• 卷：358
• 期：5
• 页码：1581-1594
• 全文大小：585 K

文摘

Anionic Fischer-type aminocarbene complexes, [(CO)₅MC(NMe₂)CH₂]Li (M=Cr or W) react with Ph₂PCl and [Me₂(MeS)S][BF₄] aaa a source of SMe⁺ aaa to afford acyclic complexes (CO)₅MC(NMe₂)CH₂X (X=PPh₂, SMe₂) and (CO)₅MC(NMe₂)CHX₂ X=SMe), the chelates and, and the bridged compounds (CO)₅MC(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 carbeneaaaphosphine and carbeneaaathioether four-membered chelates for the first time. The sulfur-donor in the tetracarbonyl complexes, and shows an exceptionally weak trans influence.