Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

Abstract

Decarbonylation along with P‐atom transfer from the phosphaethynolate anion, PCO−, 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 phosphanylidene phosphorane complex [(PNPP)NbCl(NtBuAr)] (2). Reduction of 2 with CoCp*2 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). Theoretical studies have been used to understand both the coupling of the P‐atom and the reductive cleavage of the P−P bond. Reaction of 3 with a two‐electron oxidant such as ethylene sulfide results in a diamagnetic sulfido complex having a P−P coupled ligand, namely [(PNPP)Nb=S(NtBuAr)] (4).