Search for: All records

Abstract The ability of B atoms on two different molecules to engage with one another in a noncovalent diboron bond is studied by ab initio calculations. Due to electron donation from its substituents, the trivalent B atom of BYZ₂(Z=CO, N₂, and CNH; Y=H and F) has the ability to in turn donate charge to the B of a BX₃molecule (X=H, F, and CH₃), thus forming a B⋅⋅⋅B diboron bond. These bonds are of two different strengths and character. BH(CO)₂and BH(CNH)₂, and their fluorosubstituted analogues BF(CO)₂and BF(CNH)₂, engage in a typical noncovalent bond with B(CH₃)₃and BF₃, with interaction energies in the 3–8 kcal/mol range. Certain other combinations result in a much stronger diboron bond, in the 26–44 kcal/mol range, and with a high degree of covalent character. Bonds of this type occur when BH₃is added to BH(CO)₂, BH(CNH)₂, BH(N₂)₂, and BF(CO)₂, or in the complexes of BH(N₂)₂with B(CH₃)₃and BF₃. The weaker noncovalent bonds are held together by roughly equal electrostatic and dispersion components, complemented by smaller polarization energy, while polarization is primarily responsible for the stronger ones. 

Abstract The replacement of a CH group of benzene by a triel (Tr) atom places a positive region of electrostatic potential near the Tr atom in the plane of the aromatic ring. This σ‐hole can interact with an X lone pair of XCCH (X=F, Cl, Br, and I) to form a triel bond (TrB). The interaction energy between C₅H₅Tr and FCCH lies in the range between 2.2 and 4.4 kcal/mol, in the order Tr=B+cation above the ring pulls density toward itself and thus magnifies the Tr σ‐hole. The TrB to the XCCH nucleophile is thereby magnified as is the strength of the TrB. This positive cooperativity is particularly large for Tr=B.