Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)
Shuruthi Senthil, Seongyeon Kwon, Dominik Fehn, Hoyoung Im, Michael R. Gau, Patrick J. Carroll, Mu‐Hyun Baik, Karsten Meyer, Daniel J. Mindiola
Abstract
Abstract Decarbonylation along with P‐atom transfer from the phosphaethynolate anion, PCO − , to the Nb IV complex [(PNP)NbCl 2 (N t BuAr)] ( 1 ) (PNP=N[2‐P i Pr 2 ‐4‐methylphenyl] 2 − ; Ar=3,5‐Me 2 C 6 H 3 ) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phosphanylidene phosphorane complex [(PNPP)NbCl(N t BuAr)] ( 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(N t BuAr)] ( 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(N t BuAr)] ( 4 ).