A Comprehensive Experimental and Theoretical Study on the [{(η(5)-C(5)H(5))(2)Zr[P(µ-PNEt(2))(2)P(NEt(2))(2)P]}](2)O Crystalline System

The structure of tetraphosphetane zirconium complex C(52)H(100)N(8)OP(10)Zr(2) 1 was determined by single crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c, with a = 19.6452(14), b = 17.8701(12), c = 20.7963(14)Å, α = γ = 90°, β = 112.953(7)°, V = 6722.7(8)Å3, Z = 4. The electronic structure of the organometallic complex has been characterized within the framework of Quantum Chemical Topology. The topology of the Electron Localization Function (ELF) and the electron density according to the Quantum Theory of Atoms in Molecules (QTAIM) show no covalent bonds involving the Zr atom, but rather dative, coordinate interactions between the metal and the ligands. This is the first reported case of a Zr complex stabilized by an oxide anion, anionic cyclopentadienyl ligands and rare tetraphosphetane anions.