Unexpected crown thioether complexation of vanadium(IV): isolation and structural characterisation of [VOCl2([9]aneS3)]([9]aneS3= 1,4,7-trithiacyclononane)

Abstract

Contrary to hard and soft acid-base predictions the ‘soft’ crown thioether [9]aneS₃ forms a stable 1 : 1 coordination complex with the extremely ‘hard’ vanadyl ion; [VOCl₂([9]aneS₃)] has a distorted octahedral structure with facial coordination (endodentate) of the trithiamacrocycle in a [2 + 1] bonding pattern, and provides the first example of a chelated high-valent group V–thioether complex.