An Anionic Vanadium Thionitrosyl Complex Supported by an Anilide-Bis(aryloxide) Ligand

Reaction of [{K(dme)}{(ONO)V≡N}]₂ ([ONO]^3- = anilide-bis(aryloxide)) with elemental sulfur afforded an anionic thionitrosyl complex [K(dme)₄][(ONO)V(NS)], which could be isolated as a dark red solid. The solid-state metrical parameters suggest that it is best described with a thio-imido resonance form. The thionitrosyl complex was shown to react with a variety of substrates at the thionitrosyl sulfur atom and across the V-N bond. Reaction with PPh₃ occurred with sulfur atom transfer to form the nitride and SPPh₃. The thionitrosyl complex underwent S-alkylation with alkyl halides to form a sulfenylimido complex [(ONO)V(NSR)] (R = Me, CH₂C₆H₄-4-Me). Reactions with Me₃SiCl and BPh₃ resulted in the formation of [(ONO)V(NSiMe₃)] and [K(dme)₄][(ONO)V(NBPh₃)] along with concomitant loss of sulfur. When treated with CO₂, CS₂, and PhNCS, the reactions took place across the V-N bond to generate [(ONO)VE] (E = O, S). The thionitrosyl complex was unstable in toluene and underwent dimerization via loss of K₂S to afford [{(ONO)V}₂(μ-NSN)]. Reaction of the thionitrosyl complex with [Cp₂Fe][PF₆] gave a mixture of products containing the NSN complex and [{(ONO)V}₂(μ-NSSN)].