Issue 6, 1984

Sulphur-containing metal complexes. Part 9. Synthesis of trisubstituted aminocarbene–thioether chelates of chromium(0) and tungsten(0)

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[double bond, length as m-dash][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.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1984, 1041-1045

Sulphur-containing metal complexes. Part 9. Synthesis of trisubstituted aminocarbene–thioether chelates of chromium(0) and tungsten(0)

J. C. Viljoen, S. Lotz, L. Linford and H. G. Raubenheimer, J. Chem. Soc., Dalton Trans., 1984, 1041 DOI: 10.1039/DT9840001041

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