Cramer Christopher J, Tolman William B
Department of Chemistry, Supercomputer Institute, and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55410, USA.
Acc Chem Res. 2007 Jul;40(7):601-8. doi: 10.1021/ar700008c. Epub 2007 Apr 26.
Using interwoven experimental and theoretical methods, detailed studies of several structurally defined 1:1 Cu-O 2 complexes have provided important fundamental chemical information useful for understanding the nature of intermediates involved in aerobic oxidations in synthetic and enzymatic copper-mediated catalysis. In particular, these studies have shed new light on the factors that influence the mode of O 2 coordination (end-on vs side-on) and the electronic structure, which can vary between Cu(II)-superoxo and Cu(III)-peroxo extremes.
通过交织运用实验和理论方法，对几种结构明确的1:1铜-氧2配合物进行的详细研究，提供了重要的基础化学信息，有助于理解合成及酶促铜介导催化中需氧氧化所涉及中间体的性质。特别是，这些研究为影响氧2配位模式（端基配位与侧基配位）和电子结构的因素带来了新的认识，其电子结构在Cu(II)-超氧和Cu(III)-过氧两种极端情况之间会有所不同。
