One-Electron Bonds in Frustrated Lewis Pair TPB Ligands: Boron Behaving as a Lewis Base.

摘要: Owing to its versatility in synthetic chemistry, TPB (tris[2-diisopropylphospino)phenyl]borane) is a very important frustrated Lewis Pair. The unusual stability of the neutral radical (TPB)Cu has been related presence one-electron B-Cu bond. Herein we show, through use different computational chemistry methods, that existence and nature this kind A⋅⋅⋅M bond (A=donor atom, M=transition metal) depends on surrounding chemical structure, can be genuine sigma bonds only if appropriate metal ligands (Y), able trap charge desired region, are chosen. This ability modulated by subtle balance between electronegativity atoms along A⋅⋅⋅M⋅⋅⋅Y paths. Most importantly, contrary many complexes which boron acts as acid, one-electron-bond-containing structures behaves base.