The Role of the Secondary Coordination Sphere in Metal-Mediated Dioxygen Activation
The Role of the Secondary Coordination Sphere in Metal-Mediated Dioxygen Activation
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发表时间：
2012
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通讯作者：
Ryan L. Shook;A. Borovik
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作者：
Ryan L. Shook;A. Borovik
Alfred Werner在近100年前提出，二次配位球在决定过渡金属络合物的物理性质中起着作用。我们现在知道，二次配位球几乎影响过渡金属化学的所有方面，包括金属介导的过程中的反应性和选择性。这些特征在过渡金属络合物对氧的结合和活化中得到了突出的体现。二次配位球的控制与金属络合物1)可逆地与氧结合或2)结合并活化氧形成高活性的M-oxo络合物的能力之间有明显的联系。在这篇论坛文章中，提出了几个生物和合成的例子，并从结构-功能关系的角度进行了讨论。特别强调具有确定的非共价相互作用的系统，例如涉及二氧衍生配体的分子内氢键。为了进一步说明这些影响，描述了M-氧代与碱性氧代配体的C-H键的均裂裂解。
Alfred Werner proposed nearly 100 years ago that the secondary coordination sphere has a role in determining 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 the 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 M–oxo complexes. In this forum article, several biological and synthetic examples are presented and discussed in terms of structure-function relationships. Particular emphasis is given to systems with defined non-covalent interactions, such as intramolecular hydrogen bonds involving dioxygen-derived ligands. To further illustrate these effects, the homolytic cleavage of C–H bonds by M– oxo complexes with basic oxo ligands is described.