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Molecular Electronic Structures of Transition Metal Complexes I pp 119–153Cite as

Biological Outer-Sphere Coordination

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Part of the book series: Structure and Bonding ((STRUCTURE,volume 142))

Abstract

The concept of outer-sphere coordination (OSC) is surveyed in the context of bioinorganic chemistry. A distinction is made between electronic and structural OSC, both arising from the interaction of the protein matrix with inner sphere ligands. Electronic OSC entails the electronic interaction between the polypeptide and inner-sphere ligands. These effects principally arise from hydrogen-bonding interactions, though through-space dipolar interactions are also encountered. Structural OSC comprises primarily steric effects that do not necessarily impact ligand electronics but rather influence inner sphere topology. Additionally, the protein matrix can be envisioned as a local “solvent” whose bulk dielectric and point charges influence the metal center. Recurring themes are highlighted where OSC regulates the properties of various metalloproteins distinguished by cofactors and/or function. Finally, cases are presented where OSC has guided molecular design.

“With some exaggeration it might be said that the model builder who finally would succeed in mimicking a biological metal centre, stands a fair chance of finding that he has synthesized not only the metal centre but the protein matrix as well.” G.W. Canters and G. Gilardi

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Acknowledgments

I have my thesis advisor Harry B. Gray to thank for my participation in this memorial to C.J. Ballhausen. Among other things, Harry guided me through the formulation of the ligand field theory, which required careful and thorough reading of Ballhausen’s opus Introduction to Ligand Field Theory. Ultimately, I largely failed to find a place for LFT in my graduate work, which in the end concerned the above topic of OSC. However, my efforts were rewarded with the opportunity to meet Ballhausen, who regarded me as a “poor chap” for having endured Introduction and made amends with Carlsberg lager and ginger cookies. Jeffrey Warren, Joshua Palmer, and Stephen Sproules provided useful comments on this manuscript. Finally, my postdoctoral advisor Serena DeBeer is gratefully acknowledged for reading this manuscript and for financial support.

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  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    Kyle M. Lancaster

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  1. Kyle M. Lancaster
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Correspondence to Kyle M. Lancaster .

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  1. St. Edmund Hall, Oxford, OX1 4AR, United Kingdom

    David Michael P. Mingos

  2. The Royal Institution of Great Britain, Albermarle Street 21, London, W1X 4BS, United Kingdom

    Peter Day

  3. Technical University of Denmark, Copenhagen, Denmark

    Jens Peder Dahl

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Lancaster, K.M. (2011). Biological Outer-Sphere Coordination. In: Mingos, D., Day, P., Dahl, J. (eds) Molecular Electronic Structures of Transition Metal Complexes I. Structure and Bonding, vol 142. Springer, Berlin, Heidelberg. https://doi.org/10.1007/430_2011_49

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