Журнал "Макрогетероциклы"

Radu Silaghi-Dumitrescu^@

“Babes-Bolyai” University, Department of Chemistry, Cluj-Napoca RO-40028, Romania

^@ E-mail: rsilaghi@chem.ubbcluj.ro 

Macrogeterocycles, 2008 1(1) 79-81

Mononuclear ferric-oxo moieties are known in non-heme environments, and have been proposed as reaction intermediates in some hemoproteins. Recently, such hemoprotein adducts have been detected spectroscopically via low-temperature cryoradiolytic reduction of their FeIV-oxo counterparts. Here computational results (UBP86/6- 31G**) are shown indicating that the electronic structures of such adducts are well described as S=1 FeIV-oxo coupled to a porphyrin radical, as opposed to the clean ferric state predicted at the same level of theory (and demonstrated experimentally) for the non-heme systems.