Role of the secondary coordination sphere in metal-mediated dioxygen activation.

ABSTRACT: Alfred Werner proposed nearly 100 years ago that the secondary coordination sphere has a role in determining the physical properties of transition-metal complexes. We now know that the secondary coordination sphere impacts nearly all aspects of transition-metal chemistry, including the reactivity and selectivity in metal-mediated processes. These features are highlighted in the binding and activation of dioxygen by transition-metal complexes. There are clear connections between control of the secondary coordination sphere and the ability of metal complexes to (1) reversibly bind dioxygen or (2) bind and activate dioxygen to form highly reactive metal-oxo complexes. In this Forum Article, several biological and synthetic examples are presented and discussed in terms of structure-function re

SUBMITTER: Shook RL 

PROVIDER: S-EPMC3417154 | biostudies-literature | 2010 Apr

REPOSITORIES: biostudies-literature