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

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Materials Science

Background:

• Vanadium nitride complexes are important precursors in inorganic synthesis.
• Thionitrosyl ligands offer unique reactivity pathways in coordination chemistry.

Purpose of the Study:

• To synthesize and characterize a novel anionic thionitrosyl vanadium complex.
• To investigate the reactivity of the thionitrosyl ligand and the V-N bond.
• To explore potential applications in sulfur and nitrogen transfer reactions.

Main Methods:

• Reaction of [{K(dme)}{(ONO)V≡N}]₂ with elemental sulfur.
• Isolation and characterization of the anionic thionitrosyl complex [K(dme)₄][(ONO)V(NS)].
• Investigation of reactions with various electrophiles (PPh₃, alkyl halides, Me₃SiCl, BPh₃, CO₂, CS₂, PhNCS) and oxidizing agents ([Cp₂Fe][PF₆]).

Main Results:

• Successful synthesis of the dark red anionic thionitrosyl complex [K(dme)₄][(ONO)V(NS)].
• Demonstrated reactivity at the thionitrosyl sulfur atom, including sulfur atom transfer to PPh₃ and S-alkylation with alkyl halides.
• Reactions across the V-N bond with CO₂, CS₂, and PhNCS to form [(ONO)VE] (E=O, S).
• Observed dimerization and decomposition pathways in toluene and with [Cp₂Fe][PF₆].

Conclusions:

• The synthesized thionitrosyl vanadium complex exhibits diverse reactivity, acting as a sulfur and nitrogen source.
• The complex's behavior is influenced by the reaction conditions and substrates, leading to various functionalized vanadium species.
• This work expands the synthetic utility of vanadium thionitrosyl complexes in inorganic chemistry.