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

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

doi:10.3390/molecules26237282

Abstract

The structure of tetraphosphetane zirconium complex C52H100N8OP10Zr2 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.

Highlights

Results andScheme 1 [12] shows the similar reaction of [Cp2HfCl2] with (Et2N)2P-P(SiMe3)Li, yielding almost solely the related phosphetane
The quantum chemical analysis of Becke and Edgecombe’s Electron Localization Function (ELF) [25] is an appealing procedure that provides a straightforward connection between the electron density distribution and the chemical structure [26,27]
In order to complement the topological analysis of the ELF and clarify the bonding pattern of 10, the topology of the electron density distribution was analyzed within the Quantum Theory of Atoms in Molecules (QTAIM) [23,24]

Summary

Results and

Scheme 1 [12] shows the similar reaction of [Cp2HfCl2] with (Et2N)2P-P(SiMe3)Li, yielding almost solely the related phosphetane. Reactions of lithium derivatives of diphosphanes (Et2N)2PP(SiMe3)Li with metalocene i Pr) yielding a phosphanylphosphido. ZrCp moieties one molecule, CpCp 3)Li involving iPr2), pointed to in iPr2N)2PP(SiMe. 3) mixture and Dimeric complex 1 incorporated two ZrCp2 moieties in one molecule, CpCp studies, we often isolate. (1)CpCp*ZrCl used in of the(Etreaction (1) 3 (Li) yielding complex 1, LiCl and (Et2 N) PP(SiMe3 ) (Scheme 2). The step is the reaction of (Cl)Cp2Zr-O-ZrCp2(Cl) with the phosphetane and an 2 + Cp*2ZrCl excess of (Et2N)2PPSiMe3(Li) yielding complex. The step is the reaction of (Cl)Cp2Zr-O-ZrCp2(Cl) with the phosphetane and an excess of (Et2N)2PPSiMe3(Li) yielding complex 1, LiCl and (Et2N)2PP(SiMe3) (Scheme 2)

Experiments with

Geometrical Analysis of Complex 1 and Reduced Model 10

Method

ELF Topological Analysis of 10

YZinare

QTAIM Analysis of 10

Synthesis

MaterialsCrystallographic and Methods

X-ray Crystallography

Computational

Conclusions