Positively charged crown thioether complexes trans-[Mo(CO)2(syn-Me9[16]aneS4)][OSO2CF3] and trans-[Mo(CO)(OSO2CF3)(syn-Me8H[16]aneS4)]; difference in π acceptor ability between tertiary and secondary sulfonium ions

Abstract

S-Methylation of trans-[Mo(CO)₂(syn-Me₈[16]aneS₄)](Me₈[16]aneS₄= 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetrathiacyclohexadecane) with MeOTf (OTf = trifluoromethylsulfonate) gives trans-[Mo(CO)₂(syn-Me₉[16]aneS₄)]OTf, while S-protonation with HOTf proceeds with evolution of CO to afford trans-[Mo(COMOTf)(syn-Me₈H[16]aneS₄)]; the structure of the crown thioether complex containing a tertiary sulfonium ion is elucidated by a single crystal X-ray diffraction study.