A Planar Ti 2 P 2 Core Assembled by Reductive Decarbonylation of − O−C≡P and P−P Radical Coupling

The complex [(nacnac)Ti(OAr)] 2 (μ 2 :η 2 ,η 2 ‐P 2 ) ( 1 ) is formed via reductive decarbonylation of the phosphaethynolate ion − [OCP], which serves as a P atom source. Complex 1 is the first structurally characterized Group 4 transition metal P 2 complex and its structure reveals the rhombic Ti 2 P 2 core is essentially planar with short bond lengths suggesting some degree of multiple bonding character between the Ti–P and P–P sites. Computational studies of 1 provide an understanding of the Ti 2 P 2 core as well as the origin of the highly downfield 31 P NMR spectroscopic signal.