Probing the Isolobal Relation between Cp′′′NiP3 and White Phosphorus by Experimental Charge Density Analysis

Author:

Meurer Florian1ORCID,Kleemiss Florian12ORCID,Riesinger Christoph1,Balázs Gábor1ORCID,Vuković Vedran13,Shenderovich Ilya G.1ORCID,Jelsch Christian3,Bodensteiner Michael1ORCID

Affiliation:

1. Faculty for Chemistry and Pharmacy University of Regensburg Universitätsstraße 31 93053 Regensburg Germany

2. Institute for Inorganic Chemistry RWTH Aachen Landoltweg 1a 52074 Aachen Germany

3. Cristallographie Résonance Magnétique et Modélisations CNRS UMR 7036 Institut Jean Barriol CNRS Université de Lorraine BP 70239 F54506 Vandoeuvre-lès-Nancy CEDEX France

Abstract

AbstractAn in‐depth analysis of the description of bonding within Cp′′′Ni‐cyclo‐P3 (Cp′′′=1,2,4‐tri‐tert‐butylcyclopentadienyl, [Ni]P3) employing X‐ray diffraction based multipolar modeling, density functional theory (DFT) as well as an “experimental wavefunction” obtained from X‐ray restrained wavefunction (XRW) fitting is presented. The results are compared to DFT calculations on white phosphorus – an isolobal analogue to [Ni]P3. A complementary bonding analysis shows insights into the reactivity of [Ni]P3. The isolobal principle is reflected in every aspect of our analysis and the employed methods seamlessly predict the differences in reactivity of [Ni]P3 and P4. Crystallographic modeling, solid‐state NMR, and DFT calculations describe the dynamic behavior of the cyclo‐P3 unit in the title molecule.

Funder

Deutsche Forschungsgemeinschaft

Studienstiftung des Deutschen Volkes

Publisher

Wiley

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