Quantitative Theoretical Predictions and Qualitative Bonding Analysis of the Divinylborinium System and Its Al, Ga, In, and Tl Congeners.

A substituted divinylborinium cation was synthesized recently and characterized crystallographically as a gauche structure with a 153° C1-C2-C3-C4 dihedral angle. A full theoretical geometrical optimization of the bis(2-mesityl-1,2-diphenylvinyl)-borane cation shows excellent agreement with the crystal structure. However, for the parent unsubstituted divinylborinium cation, we predict a nearly 90° C1-C2-C3-C4 dihedral angle using the CCSD(T)/cc-pVTZ coupled cluster method. The cis and trans planar geometries (0° and 180° for the C1-C2-C3-C4 dihedral angle) proved to be transition states with energy barriers of 2.8 and 2.3 kcal/mol, respectively, with respect to unimolecular conversion to the gauche equilibrium. The structures of the heavier boron group cations (Al, Ga, In, and Tl) have also been investigated here, finding even lower energy barriers (0.3-0.7 kcal/mol). After the ZPVE corrections, the barriers are further decreased. The torsional angles for the unknown Al, Ga, In, and Tl dimesityl substituted compounds should be somewhat less than 153°. Many of these findings may be understood in terms of qualitative electronic structure theory. The torsional folding of borane complex, including cationic divinylborinium and elementary vinylborane (C2H3BH2) or chlorovinylborane (C2H3BHCl) precursors, are investigated with natural bond orbital (NBO) analysis to unveil the electronic origins of the torsional properties. The NBO-based descriptors are employed to systematically deconstruct complex torsional dependence into a balanced portrayal of hyperconjugative and steric effects.