Dioxygen Activation and Mandelate Decarboxylation by Iron(II) Complexes of N4 Ligands: Evidence for Dioxygen-Derived Intermediates from Cobalt Analogues

The isolation, characterization, and dioxygen reactivity of monomeric [(TPA)M^II(mandelate)]⁺(M = Fe, 1; Co, 3) and dimeric [(BPMEN)₂M^II₂(μ-mandelate)₂]²⁺(M = Fe, 2; Co, 4) (TPA = tris(2-pyridylmethyl)amine and BPMEN = N¹,N²-dimethyl-N¹,N²-bis(pyridin-2-yl-methyl)ethane-1,2-diamine) complexes are reported. The iron(II)- and cobalt(II)-mandelate complexes react with dioxygen to afford benzaldehyde and benzoic acid in a 1:1 ratio. In the reactions, one oxygen atom from dioxygen is incorporated into benzoic acid, but benzaldehyde does not derive any oxygen atom from dioxygen. While no O₂-derived intermediate is observed with the iron(II)-mandelate complexes, the analogous cobalt(II) complexes react with dioxygen at a low temperature (-80 °C) to generate the corresponding cobalt(III)-superoxo species (S), a key intermediate implicated in the initiation of mandelate decarboxylation. At -20 °C, the cobalt(II)-mandelate complexes bind dioxygen reversibly leading to the formation of μ-1,2-peroxo-dicobalt(III)-mandelate species (P). The geometric and electronic structures of the O₂-derived intermediates (S and P) have been established by computational studies. The intermediates S and P upon treatment with a protic acid undergo decarboxylation to afford benzaldehyde (50%) with a concomitant formation of the corresponding μ-1,2-peroxo-μ-mandelate-dicobalt(III) (P1) species. The crystal structure of a peroxide species isolated from the cobalt(II)-carboxylate complex [(TPA)Co^II(MPA)]⁺(5) (MPA = 2-methoxyphenylacetate) supports the composition of P1. The observations of the dioxygen-derived intermediates from cobalt complexes and their electronic structure analyses not only provide information about the nature of active species involved in the decarboxylation of mandelate but also shed light on the mechanistic pathway of two-electron versus four-electron reduction of dioxygen.