Hydrocarbon oxygenation by metal nitrite adducts: Theoretical comparison with ferryl-based oxygenation agents

Abstract

Metal nitrite adducts can, under certain conditions, insert one of their oxygen atoms into hydrocarbons. This reaction is to some extent: reminiscent: of the process whereby highvalent ferryl (formally FeIV=O) species such as compound I in hemoproteins also insert an oxygen atom into hydrocarbons. Density functional theory (DFT) data are shown here, examining the oxygenation ability of ferrous and. ferric nitrite adducts in octahedral, coordination environments modeling those seen in hemoproteins where such adducts are well characterized. A comparison of these results with those obtained with, similar methods on formal Fev-oxldo models of hemoprotein compound I models relevant for such enzymes as cytochrome P450 and chloroperoxidase reveals a key role of the redox potential in dictating oxygenation ability, in good agreement with interpretations previously given by Green and co-workers, © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.