Gold thioether chemistry: synthesis, structure, and redox interconversion of [Au([9]aneS3)2]+/2+/3+([9]aneS3= 1,4,7-trithiacyclononane)

Abstract

The crystal structure of [Au([9]aneS₃)₂]PF₆ shows distorted tetrahedral S₄ co-ordination at Au^I with one [9]aneS₃ bound in a unidentate manner [Au(1)–S(11) 2.302(6)Å], and the other bound asymmetrically through three S-donors [Au(1)–S(21) 2.350(7), Au(1)–S(24) 2.733(8), Au(1)–S(27) 2.825(8)Å]; oxidation of this complex affords the Au^III analogue [Au([9]aneS₃)₂]³⁺ which has a distorted octahedral stereochemistry [Au(1)⋯ S(1) 2.926(4), Au(1)–S(4) 2.348(4), Au(1)–S(7) 2.354(4)Å]; the intermediate paramagnetic Au^III species has been identified by e.s.r. spectroscopy.