Stabilization of Boron–Boron Triple Bonds by Mesoionic Carbenes

[Image: see text] Density functional theory-based computations are carried out to analyze the electronic structure and stability of B(2)(MIC)(2) complexes, where MIC is a mesoionic carbene, viz., imidazolin-4-ylidenes, pyrazolin-4-ylidene, 1,2,3-triazol-5-ylidene, tetrazol-5-ylidene, and isoxazol-4-ylidene. The structure, stability, and the nature of bonding of these complexes are further compared to those of the previously reported B(2)(NHC)(2) and B(2)(cAAC)(2). A thorough bonding analysis via natural bond order, molecular orbital, and energy decomposition analyses (EDA) in combination with natural orbital for chemical valence (NOCV) reveals that MICs are suitable ligands to stabilize B(2) species in its (3)(1)∑(g)(+) excited state, resulting in an effective B–B bond order of 3. Their high dissociation energy and endergonicity at 298 K for the dissociations L–BB–L → 2 B–L and L–BB–L → BB + 2 L (L = Ligand) indicate their viability at ambient condition. The donor property of MICs is comparable to that of NHC(Me). The orbital interaction plays a greater role than the coulombic interaction in forming the B–L bonds. The EDA-NOCV results show that the sum of the orbital energies associated with the (+, +) and (+, −) L→[B(2)]←L σ-donations is far larger than that of L←[B(2)]→L π-back donation. It also reveals that cAAC(Me) possesses the largest σ-donation and π-back donation abilities among the studied ligands, and the σ-donation and π-back donation abilities of MICs are comparable to those of NHC(Me). Therefore, the present study shows that MICs would also be an excellent choice as ligands to experimentally realize new compounds having a strong B–B triple bond.