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

Chemistry - A European Journal, vol. 30, pp. e202303762

Abstract

Abstract An 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.

Authors 7

1. Florian Meurer

   University of Regensburg

   Affiliation as printed

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

2. Florian Kleemiss Aachen Institute for Inorganic Chemistry

   University of Regensburg · RWTH Aachen University

   Affiliation as printed

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

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

3. Gábor Balázs

   University of Regensburg

   Affiliation as printed

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

4. Vedran Vuković

   Centre National de la Recherche Scientifique · Laboratoire de Cristallographie, Résonance Magnétique et Modélisations · University of Regensburg · Université de Lorraine

   Affiliation as printed

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

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

5. Ilya G. Shenderovich

   University of Regensburg

   Affiliation as printed

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

6. Christian Jelsch

   Centre National de la Recherche Scientifique · Laboratoire de Cristallographie, Résonance Magnétique et Modélisations · Université de Lorraine

   Affiliation as printed

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

7. Michael Bodensteiner corresponding

   University of Regensburg

   Affiliation as printed

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