The vanadium(ii) complex is shown to mediate reductive oligomerization of aryl isocaynides, leading to formation of a dimer, trimers, and tetramers. The analogous reaction with alkyl isocyanides results in C–NC bond cleavage.
Here we show that a tridentate bis(aryloxide)anilide-ligated titanium/potassium scaffold promotes functionalization of coordinated N 2 with CO 2 and CS 2 through formation of NÀ C bonds. Treatment of a naphthalene complex with N 2 gave an end-on bridging dinitrogen complex featuring a [Ti 2 K 2 N 2 ] core. The dinitrogen complex underwent insertion of CO 2 into each TiÀ NN bond to afford an N,N'-dicarboxylated hydrazido complex. Stepwise nitrogen-carbon bond formation at coordinated N 2 proceeded to afford an unsymmetric hydrazido complex upon sequentially treating the dinitrogen complex with CS 2 and CO 2 . Addition of Me 3 SiCl to the dicarboxylated hydrazido complex resulted in partial silylation of the carboxylate groups but did not lead to removal of the functionalized N 2 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.
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.
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