C[double bond, length as m-dash]O scission and reductive coupling of organic carbonyls by a redox-active diboraanthracene.

Abstract

The boron-centered reactivity of the diboraanthracene-auride complex [Au(B2P2)][K(18-c-6)]; (B2P2, 9,10-bis(2-(diisopropylphosphino)-phenyl)-9,10-dihydroboranthrene) with a series of organic carbonyls is reported. The reaction of [Au(B2P2)]- with formaldehyde or paraformaldehyde results in a head-to-tail dimerization of two formaldehyde units across the boron centers. In contrast, the reaction of [(B2P2)Au]- with two equivalents of benzaldehyde yields the pinacol coupling product via C-C bond formation. Careful stoichiometric addition of one equivalent of benzaldehyde to [Au(B2P2)]- enabled the isolation of an adduct corresponding to the formal [4+2] cycloaddition of the C[double bond, length as m-dash]O bond of benzaldehyde across the boron centers. This adduct reacts with a second equivalent of benzaldehyde to produce the pinacol coupling product. Finally, the reaction of [Au(B2P2)]- with acetone results in a formal reductive deoxygenation with discrete hydroxo and 2-propenyl units bound to the boron centers. This reaction is proposed to proceed via an analogous [4+2] cycloadduct, highlighting the unique small molecule activation chemistry available to this platform.