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Hydrocarbon Oxygenation by Metal Nitrite Adducts: Theoretical Comparison with Ferryl‐Based Oxygenation Agents
Author(s) -
SilaghiDumitrescu Radu,
Makarov Sergei V.
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200901044
Subject(s) - chemistry , adduct , hemeprotein , nitrite , ferrous , photochemistry , metal , oxygen , myoglobin , ferric , redox , heme , inorganic chemistry , organic chemistry , enzyme , nitrate
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 high‐valent ferryl (formally Fe IV =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 Fe V –oxido 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.