Abstract
Anionic Fischer-type aminocarbene complexes, [(CO) 5M C(NMe 2)CH 2]Li (M = Cr or W) react with Ph 2PCl and [Me 2(MeS)S][BF 4] – a source of SMe + – to afford acyclic complexes (CO) 5M C(NMe 2)CH 2X (X = PPh 2, SMe 2) and (CO) 5M C(NMe 2)CHX 2 X = SMe), the chelates ▪ and ▪, and the bridged compounds (CO) 5M C(NMe 2)CH 2XM(CO) 5 (X = PPh 2, 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 ▪, and ▪ shows an exceptionally weak trans influence.
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