C–H Activation of co-ordinated crowns thioethers: deprotonation and ring-opening of [M([9]aneS3)2]3+(M = Co, Rh, Ir). Crystal structure of [Rh(H2CCHS(CH2)2S(CH2)2S)([9]aneS3)](PF6)2([9]aneS3= 1,4,7-trithiacyclononane)

Abstract

Addition of base to the complexes [M([9]aneS₃)₂]³⁺([9]aneS₃= 1,4,7-trithiacyclononae; M = Co, Rh, Ir) leads to deprotonation at a methylene carbon, and subsequent re-arrangement of the carbanion affords a vinyl thioether complex via C–S bond cleavage; for M = Co this process is reversed in acidic medium to regenerate [Co([9]aneS₃)₂]³⁺.