A Planar Ti2 P2 Core Assembled by Reductive Decarbonylation of - O-C≡P and P-P Radical Coupling.

The complex [(nacnac)Ti(OAr)]2 (μ2 :η2 ,η2 -P2 ) (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 P2 complex and its structure reveals the rhombic Ti2 P2 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 Ti2 P2 core as well as the origin of the highly downfield 31 P NMR spectroscopic signal.