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1 TASK Quarterly : scientific bulletin of Academic Computer Centre in Gdansk

1 2014

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Spin and electron density redistribution upon binding of non-innocent ligand by iron in enzymatic environment: challenges for quantum chemistry

Brocławik E., Borowski T., Radoń M.

TASK Quarterly : scientific bulletin of Academic Computer Centre in Gdansk

2014

Vol. 18, No 3

255--263

The quality of the description of a chemical bond between the metal (acti ve site) and the ligand (substrate) critically depends on the electronic pro cesses accompanying the bond formation. However, as far as transition metal centers ( TM ) in enzymes are considered, most of the properties related to their electronic structure are extre mely challenging for quantum chemistry. Especially severe problems appear for the bonding of NO to fe rrous sites, e.g. in myoglobin or non-heme enzymes. Therefore, special care has to be shown in t he assessment of a quantum chemical method employed with respect to its power in des cribing the properties of interest. In this work we discuss spin-resolved Fe-NO charge transfe rs and their relation to the metal spin state, with special attention paid to the interpretation of t he bonding between NO and the transition metal center in terms of dative or covalent contributi ons; furthermore, the impact of spin and the electron transfer on the reactivity of the center is discussed. The stress is put on the role of the coordinating environment in controlling the re action mechanism via fine-tuning of the spin and the oxidation status of the metal core. This goe s in line with the high significance of spin in enzymatic reaction mechanisms ( cf. multi-state reactivity proposed for iron enzymes).