Abstract
Several isocyanide–thioether complexes, cis-[M(CNR)(CO)4{S(R1)CH2R2}][M = Cr: R = But, R1R2=(CH2)3S; R = R1= Ph, R2= SPh; R = cyclo -C6H11 or CH2Ph, R1R2=(CH2)3S. M = W : R = But, R1R2=(CH2)3S] were prepared by u.v. irradiation of the corresponding pentacarbonyl(isocyanide) complexes in the presence of the thioether compounds. Deprotonation of two of these, cis-[M(CNBut)(CO)4{[graphic omitted]H2}](M = Cr or W), with LiBu and addition of PEt3, resulted (via consecutive carbonylation and isocyanide insertion into a metal–carbene bond) in the formation of the evasive trisubstituted aminocarbene–thioether chelates, fac-[[graphic omitted]}(PEt3)], upon alkylation with [Et3O][BF4]. Replacement of the phosphine by 1,3-dithiolane-2-thione under similar reaction conditions yielded, unexpectedly, the substitution products cis-[Cr(CNR)(CO)4{S[graphic omitted]}](R = But or Ph). When in addition, the isocyanide had been substituted for CO, the first saturated cyclic dithiocarbene complex of chromium, [Cr(CO)5{[graphic omitted]}], was formed.
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