Syntheses and characterizations of trinuclear and dinuclear “half-sandwich” zirconocene phosphates and phosphonates

Abstract

A series of six-coordinate “half-sandwich” zirconocene phosphates and phosphonates have been synthesized by the reaction of Cp2ZrCl2 with (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid under different conditions. All of the complexes were characterized by elemental analysis, FT-IR and NMR (1H, 13C) spectroscopy. Except for complex 3, the structures of complexes 1, 2, 4, 5, and 6 were confirmed by X-ray crystallography. The structure analyses reveal that complexes 1, 2, and 3 are trinuclear complexes with fascinating μ3-oxygen bridging ligands, central to a Zr–O backbone (Cp2ZrCl2:ligand is 1:1) while complexes 4, 5, and 6 are centrosymmetric dinuclear complexes built up about the trapezoidal Zr2(μ2-OH)2 unit (Cp2ZrCl2:ligand is 1:2).