Abstract
Reaction of α-lithiated sulphides with (CO) 6Cr and (CO) 6W followed by alkylation with (Et 3O)BF 4 give the new series of neutral carbene-thiometal chelates of general formulae cis-(CO) 4 MC(OEt)[C(OH)C(S R 1)R 2] (I) and cis-(CO) 4 MC(OEt)[C(OEt)C(S R 1)R 2] (II). This route probably involves carbonyl insertion into a metalcarbene bond. Complexes of type II can also be prepared by treatment of pentacarbonyl(thio)metal complexes, (CO) 5MS(CH 2R 2)R 1, with BuLi, and subsequent alkylation. It is suggested that the second method proceeds via the generation of an anion α to a coordinated sulphur atom followed by a double ( cis-cis) carbonylation.
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