Building more complex molecules from simple hydrocarbons remains a subject of significant research interest today. Specifically, the activation of usually inert C-C bonds in arenes and the functionalization of unactivated C-H bonds are regarded as attractive synthetic targets. For example, the challenges in C-H activation of hydrocarbons stem from selectivity issues, and the thermodynamically disfavoured C-C cleavage in benzene has previously been achieved only by transient and highly reactive compounds generated in situ. Furthermore, the formal oxidative addition reactions of arene C-H/C-C bonds brought about by a single main group metal centre in contrast to a transition metal complex are still quite rare. In this regard, the Aldridge group reported an anionic aluminium(I) compound 1 (Figure 1) in 2018, which has been shown to react as a metal-centred nucleophile towards C-X and M-X bonds. Moreover, the dimeric aluminyl 1 oxidatively adds benzene at elevated temperatures whereas the monomeric analogue reacts reversibly with the benzene C-C bond at room temperature. In this contribution, the factors effecting this C-C bond cleavage of benzene over the formation of a phenyl hydride product will be discussed by both experimental and computational considerations. In addition, the scope and selectivity for C-H activation chemistry of 1 with substituted arenes will be explored.

Arene C-H and C-C bond activation by a nucleophilic aluminium: A combined experimental and computational study

ACS Spring 2022

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