Mild C–H functionalization of alkanes catalyzed by bioinspired copper(ii) cores

Abstract

Three new copper(II) coordination compounds formulated as [Cu(H_1.5bdea)₂](hba)·2H₂O (1), [Cu₂(μ-Hbdea)₂(aca)₂]·4H₂O (2), and [Cu₂(μ-Hbdea)₂(μ-bdca)]_n (3) were generated by aqueous medium self-assembly synthesis from Cu(NO₃)₂, N-butyldiethanolamine (H₂bdea) as a main N,O-chelating building block and different carboxylic acids [4-hydroxybenzoic (Hhba), 9-anthracenecarboxylic (Haca), or 4,4′-biphenyldicarboxylic (H₂bdca) acid] as supporting carboxylate ligands. The structures of products range from discrete mono- (1) or dicopper(II) (2) cores to a 1D coordination polymer (3), and widen a family of copper(II) coordination compounds derived from H₂bdea. The obtained compounds were applied as bioinspired homogeneous catalysts for the mild C–H functionalization of saturated hydrocarbons (cyclic and linear C₅–C₈ alkanes). Two model catalytic reactions were explored, namely the oxidation of hydrocarbons with H₂O₂ to a mixture of alcohols and ketones, and the carboxylation of alkanes with CO/S₂O₈²⁻ to carboxylic acids. Both processes proceed under mild conditions with a high efficiency and the effects of different parameters (e.g., reaction time and presence of acid promoter, amount of catalyst and solvent composition, substrate scope and selectivity features) were studied and discussed in detail. In particular, an interesting promoting effect of water was unveiled in the oxidation of cyclohexane that is especially remarkable in the reaction catalyzed by 3, thus allowing a potential use of diluted, in situ generated solutions of hydrogen peroxide. Moreover, the obtained values of product yields (up to 41% based on alkane substrate) are very high when dealing with the C–H functionalization of saturated hydrocarbons and the mild conditions of these catalytic reactions (50–60 °C, H₂O/CH₃CN medium). This study thus contributes to an important field of alkane functionalization and provides a notable example of new Cu-based catalytic systems that can be easily generated by self-assembly from simple and low-cost chemicals.