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Authorship：Lead author   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

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)].

DOI： 10.1002/chem.202501390

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/cl.230141

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Publishing type：Research paper (scientific journal)  

DOI： 10.1039/D2CC01985J

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