Oxidation of Sulfide, Phosphine, and Benzyl Substrates Tethered to N-Donor Pyridine Ligands in Carboxylate-Bridged Diiron(II) Complexes

Substituted pyridines were employed to prepare a series of terphenylcarboxylate-bridged diiron(II) compounds to mimic aspects of the chemistry at the active sites of bacterial multicomponent monooxygenases, including soluble methane monooxygenase (sMMO) and toluene monooxygenase (ToMO). Complexes of general formula [Fe2(O2CArTol)4L], L = 2, 3, or 4-pyridyldiphenylphosphine, 2-pyridylphenylsulfide, or 2-benzylpyridine and ArTol = 2,6-di(p-tolyl)benzoate, were synthesized and characterized by X-ray crystallography. Upon exposure of these compounds to dioxygen, ligand oxidation ensued and, in one case, proceeded catalytically.

本研究采用取代吡啶类化合物，制备了一系列三联苯羧酸桥联二铁(II)配合物，用以模拟细菌多组分单加氧酶活性位点的化学过程，涵盖可溶性甲烷单加氧酶（sMMO）与甲苯单加氧酶（ToMO）。通式为[Fe₂(O₂CArTol)₄L]的配合物（其中L为2-、3-或4-吡啶基二苯基膦、2-吡啶基苯基硫醚或2-苄基吡啶，ArTol为2,6-二(对甲苯基)苯甲酸根）经合成并通过X射线晶体学（X-ray crystallography）表征。将此类配合物暴露于氧气后，配体氧化反应随即发生，其中一例反应以催化方式进行。