Aliphatic Carbon-Carbon Bond Cleavage Reactivity of a Mononuclear Ni(II) cis-beta-Keto-Enolate Complex in the Presence of Base and O_2:A Model Reaction for Acireductone Dioxygenase(ARD)

摘要

This report describes the synthesis,characterization,and aliphatic carbon-carbon bond cleavage reactivity of a Ni(II)cis-beta-keto- enolate complex,[(6-Ph_2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO_4(1,6-Ph_2TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)-methyl)amine).In the presence of 1 equiv of base and O)_2,1 undergoes reaction to produce [(6-Ph_2TPA)Ni(O_2CPh)_2(H_2O)](2)and CO.Metal-containing dioxygenases catalyze the incorporation of both oxygen atoms of O_2 into one or more substrates.Examples include Rieske and catechol dioxygenases,which catalyze oxidative hy-droxylation and ring-opening reactions of aromatic substrates,respectively,and typically have a nonheme iron center.Recently,examples of dioxygenases that catalyze oxidative aliphatic carbon-carbon bond cleavage have been reported.