Publishing type：Research paper (scientific journal)   Publisher：Wiley  

Abstract

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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Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

Stepwise methylation of end-on bridging dinitrogen to a hydrazido ligand to a pentamethylhydrazinium salt is mediated by a titanium complex.

DOI： 10.1039/d4cc02080d

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Publishing type：Research paper (scientific journal)   Publisher：Wiley  

Abstract

Here we show that a tridentate bis(aryloxide)anilide‐ligated titanium/potassium scaffold promotes functionalization of coordinated N₂ with CO₂ and CS₂ through formation of N−C bonds. Treatment of a naphthalene complex with N₂ gave an end‐on bridging dinitrogen complex featuring a [Ti₂K₂N₂] core. The dinitrogen complex underwent insertion of CO₂ into each Ti−NN bond to afford an N,N′‐dicarboxylated hydrazido complex. Stepwise nitrogen‐carbon bond formation at coordinated N₂ proceeded to afford an unsymmetric hydrazido complex upon sequentially treating the dinitrogen complex with CS₂ and CO₂. Addition of Me₃SiCl to the dicarboxylated hydrazido complex resulted in partial silylation of the carboxylate groups but did not lead to removal of the functionalized N₂ unit from the metal centers. However, reduction of the dicarboxylated hydrazido complex with potassium naphthalenide afforded an oxo‐bridged dinuclear complex along with release of free potassium cyanate.

DOI： 10.1002/anie.202304700

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