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

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.

Keywords: Isolobal relationship; NMR spectroscopy; Quantum Chemistry; Structure elucidation; X-ray diffraction.