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Electrophilic and nucleophilic reactions of complexes formed from 2,5-dithiahex-3-yne (MeSCCSMe) and tungsten carbonyls

Authors
Journal
Journal of Organometallic Chemistry
0022-328X
Publisher
Elsevier
Publication Date
Volume
394
Identifiers
DOI: 10.1016/0022-328x(90)87235-6

Abstract

Abstract The alkyne, MeSCCSMe, reacts with tungsten(II) carbonyl complexes to yield π-alkyne products, CpW(η 2-MeSCCSMe) 2Cl ( 1), W(CO)(η 2-MeSCCSMe)(S 2CNR 2) 2 (R = Me ( 2a) and Et ( 2b)), and W(η 2-MeSCCSMe) 2(S 2CNR 2) 2 (R = Me ( 3a) and Et ( 3b)). The sulfonium complex [CpClW(η 2-MeSCCSMe)(η 2-MeSCCSMe 2)]BF 4 ( 4), whose structure was established by an X-ray diffraction study, was prepared by the reaction of 1 with Me 3O +. The Cp(PMe 3) 2Ru + group also adds to a sulfur in 1 to give {CpClW(η 2-MeSCCSMe)[η 2-MeSCCS(Me)Ru(PMe 3) 2Cp]}BF 4 ( 5). Nucleophilic attack by H − donors and RS − on 4 displaces Me 2S to yield CpW(η 2-MeSCCSMe)(η 2-MeSCCX)Cl (X = H ( 6), SC 6H 5 ( 7a), and 4-SC 6H 4Me ( 7b)) and Me 2S.

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