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

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Computational Chemistry

Background:

• The cyclo-triphosphorus ligand is a key component in various organometallic complexes.
• Understanding the electronic structure and bonding in these complexes is crucial for predicting reactivity.

Purpose of the Study:

• To investigate the bonding and electronic structure of Cp'''Ni-cyclo-P3 ([Ni]P3).
• To compare the properties of [Ni]P3 with its isolobal analogue, white phosphorus (P4).
• To elucidate the factors governing the reactivity of [Ni]P3.

Main Methods:

• X-ray diffraction-based multipolar modeling.
• Density functional theory (DFT) calculations.
• X-ray restrained wavefunction (XRW) fitting for experimental wavefunctions.

Main Results:

• Detailed bonding analysis of the nickel-cyclo-triphosphorus system.
• DFT calculations confirm the isolobal analogy between [Ni]P3 and P4.
• Insights into the reactivity differences and similarities between [Ni]P3 and P4 were obtained.

Conclusions:

• The isolobal principle accurately describes the behavior of [Ni]P3 and P4.
• Computational methods effectively predict the reactivity patterns.
• The dynamic behavior of the cyclo-P3 unit was characterized using crystallographic modeling, solid-state NMR, and DFT.