Solomon, Edward I., Pau, Monika Y.M., and Hocking, Rosalie K. (2009) Nature of the catecholate-Fe(III) bond: high affinity bonding and substrate activation in bioinorganic chemistry. In: Solomon, Edward I., Scott, Robert A., and King, R. Bruce, (eds.) Computational Inorganic and Bioinorganic Chemistry. Encyclopedia of Inorganic Chemistry . Wiley-Blackwell, Chichester, UK, pp. 241-253.

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Abstract

[Extract] We have developed the method of metal L-edge X-ray absorption spectroscopy (XAS) as a probe of differential orbital covalency (DOC), the amount of ligand character in the different d orbitals of a metal site, in a highly covalent environment. In Section 2 of this review, we present this method and develop its information content. In Section 3, we apply this method to experimentally determine the covalency of the ligand-metal bonds in complexes related to the siderophores and computationally evaluate this contribution to their high stability constants. In Section 4, we extend these studies to the intradiol dioxygenases where variable-temperature, variable-field (VTVH) MCD experimentally defines the catecholate frontier molecular orbitals (FMO) involved in substrate activation. These are then complemented with density functional theory (DFT) calculations to evaluate the reaction coordination for catalytic dioxygenation, in particular, to evaluate how the ligand field (LF) of the Fe(III) can overcome the spin-forbidden nature of the reaction of triplet O2 with the singlet catecholate substrate.

Item ID:	34663
Item Type:	Book Chapter (Research - B1)
ISBN:	978-0-470-69997-3
Funders:	National Institute of Health (NIH), USA, National Science Foundation (NSF), USA
Projects and Grants:	NIH GM-40392, NSF CHE-0446304
Date Deposited:	25 Aug 2014 06:14
FoR Codes:	03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030201 Bioinorganic Chemistry @ 100%
SEO Codes:	97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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