Electronic Structures of Oxo-Metal Ions

Creators: Winkler, Jay R.; Gray, Harry B.

Others:: Mingos, D. M. P.; Day, P.; Dahl, Jens Peder

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Abstract

The dianionic oxo ligand occupies a very special place in coordination chemistry, owing to its ability to donate π electrons to stabilize high oxidation states of metals. The ligand field theory of multiple bonding in oxo-metal ions, which was formulated in Copenhagen 50 years ago, predicts that there must be an "oxo wall" between Fe-Ru-Os and Co-Rh-Ir in the periodic table. In this tribute to Carl Ballhausen, we review this early work as well as new developments in the field. In particular, we discuss the electronic structures of beyond-the-wall (groups 9 and 10) complexes containing metals multiply bonded to O- and N-donor ligands.

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© 2011 Springer-Verlag Berlin Heidelberg. Published online: 6 October 2011. We dedicate this paper to the memory of Carl Ballhausen, a great scientist and a dear friend (Fig. 5). We note in closing that the B&G model is providing a firm foundation for structure/reactivity correlations in our current work on oxo-metal complexes [oxidative enzymes P450 and nitric oxide synthase (NIH DK019038, GM068461): water oxidation catalysts (NSF CCI Solar Program, CHE-0947829): and trans-dioxo osmium(VI) electrochemistry and photochemistry (BP)]. We thank the Gordon and Betty Moore Foundation and the Arnold and Mabel Beckman Foundation for support of our research programs.

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Electronic Structures of Oxo-Metal Ions

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