A Comprehensive Experimental and Theoretical Study on the [{(η5-C5H5)2Zr[P(µ-PNEt2)2P(NEt2)2P]}]2O Crystalline System

Agnieszka Łapczuk-Krygier; Katarzyna Kazimierczuk; Jerzy Pikies; Mar Ríos-Gutiérrez

doi:10.3390/molecules26237282

A Comprehensive Experimental and Theoretical Study on the [{(η⁵-C₅H₅)₂Zr[P(µ-PNEt₂)₂P(NEt₂)₂P]}]₂O Crystalline System

Molecules. 2021 Nov 30;26(23):7282. doi: 10.3390/molecules26237282.

Authors

Agnieszka Łapczuk-Krygier¹, Katarzyna Kazimierczuk², Jerzy Pikies², Mar Ríos-Gutiérrez³

Affiliations

¹ Institute of Organic Chemistry and Technology, Krakow University of Technology, Warszawska St. 24, 31-155 Krakow, Poland.
² Department of Inorganic Chemistry, Faculty of Chemical, Gdansk University of Technology, G. Narutowicza St. 11/12, 80-233 Gdansk, Poland.
³ Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, 46100 Valencia, Spain.

Abstract

The structure of tetraphosphetane zirconium complex C₅₂H₁₀₀N₈OP₁₀Zr₂1 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.

Keywords: ELF; QTAIM; X-ray crystal structure; phosphetane; zirconocene.