We report the synthesis and characterization of the first neutral niobium phosphide. Decarbonylation along with P-atom transfer from OCP− to the NbIV complex [(PNP)NbCl2(NtBuAr)] (1) (PNP− = N[2-PiPr2-4-methylphenyl]2; Ar = 3,5-Me2C6H3) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phospha-Wittig pincer complex [(PNPP)NbCl(NtBuAr)] (2). Reduction of 2 with Na/NaCl cleaves the P−P bond to form the first neutral and terminal phosphido complex of a group 5 transition metal, namely, [(PNP)Nb≡P(NtBuAr)] (3). Oxidation of the phosphido ligand of 3 with 1/2PhICl2 reforms the P−P bond in 2. Electrochemical studies of 2 in combination with theoretical studies have been applied to understand the oxidative coupling and reductive cleavage of the P−P bond. Complex 3 can also react with episulfide to produce a diamagnetic sulfido having a P−P coupled ligand, namely [(PNPP)Nb=S(NtBuAr)] (4).

Metal-ligand cooperativity to assemble a neutral and terminal niobium phosphide

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