Dinuclear iron and vanadium complexes of the N(CH2CH2S)33−ligand with bridging oxide, nitride or cyanide

Abstract

Reaction of Et₄N[Fe(NS₃)(CO)] [NS₃ is the ligand N(CH₂CH₂S)₃] with trimethylamine oxide in MeCN gives (Et₄N)₂[{Fe(NS₃)}₂(μ-O)]·MeCN 1 with a symmetrical, bent Fe–O–Fe bridge while reaction of Et₄N[V(NS₃)Cl] with sodium azide gives Et₄N[{V(NS₃)}₂(μ-N)]·MeCN 2 with an unprecedented linear symmetrical V–N–V bridge. Reaction of [V(NS₃)(NH₂NH₂)] with R₄NCN salts gives R₄N[{V(NS₃)}₂(μ-CN)]·2MeCN (3, R = Et; 4, R = ⁿBu) while reaction of iron(III) acetylacetonate and Et₄NCN + Et₄NOAc with N(SH)₃ gives (Et₄N)₂[{Fe(NS₃)}₂(μ-CN)]·MeCN 5, which dissociates to Et₄N[Fe(NS₃)(CN)] 6 and an uncharacterised species in methanol. The above complexes were characterised by microanalyses, IR and magnetic measurements and where appropriate by Mössbauer and ESR spectra; X-ray structural determinations were carried out on 1, 2, 4 and 6.