Shook Ryan L, Borovik A S
Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA.
Chem Commun (Camb). 2008 Dec 14(46):6095-107. doi: 10.1039/b810957e. Epub 2008 Oct 1.
Hydrogen bonds stabilize and direct chemistry performed by metalloenzymes. With inspiration from enzymes, we will utilize an approach that incorporates intramolecular hydrogen bond donors to determine their effects on the stability and reactivity of metal complexes. Our premise is that control of secondary coordination sphere interactions will promote new function in synthetic metal complexes. Multidentate ligands have been developed that create rigid organic structures around metal ions. These ligands place hydrogen bond (H-bond) donors proximal to the metal centers, forming specific microenvironments. One distinguishing attribute of these systems is that site-specific modulations in structure can be readily accomplished, in order to evaluate correlations with reactivity. A focus of this research is consideration of dioxygen binding and activation by metal complexes, including developing structure-function relationships in metal-assisted oxidative catalysis.
氢键稳定并指导金属酶所进行的化学反应。受酶的启发，我们将采用一种纳入分子内氢键供体的方法来确定它们对金属配合物稳定性和反应活性的影响。我们的前提是，对二级配位层相互作用的控制将促进合成金属配合物产生新功能。已经开发出多齿配体，它们在金属离子周围形成刚性有机结构。这些配体将氢键供体置于靠近金属中心的位置，形成特定的微环境。这些体系的一个显著特点是，可以很容易地实现结构的位点特异性调节，以便评估与反应活性的相关性。本研究的一个重点是考虑金属配合物对双氧的结合和活化，包括建立金属辅助氧化催化中的结构-功能关系。
