锰(V)氧和亚胺配合物催化的环氧化反应：氧化剂-锰-氧（亚胺）中间体的作用。

Epoxidations catalyzed by manganese(V) oxo and imido complexes: role of the oxidant-Mn-oxo (imido) intermediate.

机构信息

Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.

出版信息

Inorg Chem. 2010 Apr 5;49(7):3083-5. doi: 10.1021/ic902517j.

PMID:20201529

Abstract

The manganese(V) oxo complex (TBP(8)Cz)Mn(V)(O) (1) is shown to catalyze the epoxidation of alkenes with a series of iodosylarenes (ArIO) as oxidants. Competition experiments reveal that the identity of ArIO influences the product ratios, implicating an unusual coordinated oxo-metal-ArIO intermediate (1-OIAr) as the active catalytic species. The isoelectronic manganese(V) imido complex (TBP(8)Cz)Mn(V)(NMes) (2) does not participate in NR transfer but does catalyze epoxidations with ArIO as the O-atom source, suggesting a mechanism similar to that seen for 1. Direct evidence (ESIMS) is obtained for 1-OIMes.

摘要

锰(V)氧配合物（TBP(8)Cz)Mn(V)(O)（1）被证明可催化烯烃与一系列碘代芳烃（ArIO）作为氧化剂的环氧化反应。竞争实验表明，ArIO 的种类影响产物比例，表明一种不寻常的配位氧-金属-ArIO 中间体（1-OIAr）是活性催化物种。等电子的锰(V)亚胺配合物（TBP(8)Cz)Mn(V)(NMes)（2）不参与 NR 转移，但可催化 ArIO 作为氧原子源的环氧化反应，表明其机制类似于 1。通过电喷雾质谱（ESIMS）直接获得了 1-OIMes 的证据。