Herein we report the discovery that two bottleable, neutral, base-stabilized diborane(5) compounds are able to bind strongly to a number of copper(I) complexes exclusively through their B-B bond. The resulting complexes represent the first known complexes containing unsupported, neutral σ diborane ligands. Single-crystal X-ray analyses of these complexes show that the X-Cu moiety (X=Cl, OTf, C F ) lies opposite the bridging hydrogen atom of the diborane and is near perpendicular to the B-B bond, interacting almost equally with both boron atoms and causing a B-B bond elongation. DFT studies show that σ donation from and π backdonation to the pseudo-π-like B-B bond account for their formation. Astoundingly, these copper σ complexes are inert to ligand exchange with pyridine under either heating or photoirradiation.
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