Toward the Chemical Structure of Diborane: Electronic Force Density Fields, Effective Electronegativity, and Internuclear Turning Surface Properties.

ABSTRACT

The chemical structure of diborane was elucidated through the superposition of the vector fields of the electron density gradient ∇ρ(r), the electrostatic force Fes(r), and the kinetic force Fk(r), together with the analysis of the cumulative charges of the atoms and pseudoatoms delimited in the aforementioned fields. It was proposed that the Fk-pseudoatomic charge could be employed as a metric for quantifying the ionic component of a related atomic charge. The electron permeability across an internuclear turning surface─specifically, the zero-flux surface in Fk(r)─was characterized by probing it through mapping the total static potential φem(r). The conceptualization of post hoc electronegativity was presented for consideration. Our analysis revealed that the ordinary B-H and bent B-µ-H bonds in diborane demonstrate the polar covalent character with minor contributions of the ionic component. The former bond exhibits a greater electron permeability through the internuclear turning surface, indicating a stronger tendency for electron sharing between the corresponding nucleus-dominated regions. The electron density accumulation along the bent B-µ-H bond path diverges from the minimum action trajectories of the forces Fes(r) and Fk(r). This phenomenon can be associated with the structural strain within the angled, three-center two-electron bonding B-µ-H-B. The internuclear B···B paths were identified in Fes(r) and Fk(r), in contrast to ∇ρ(r). This fact, in conjunction with a pronounced electron permeability through the mutual turning surface between the two boron nuclei, implies a certain degree of electron exchange between the boron-dominated pseudoatomic regions. Furthermore, the anomalous [B-]H···µ-H intermolecular polar interactions were described between the strongly negatively charged hydrogen atoms in the monoclinic crystalline ß-phase of diborane. In fact, the ionic contributions to the charges of the hydrogen atoms are shown to be relatively small.