Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex.

Abstract

Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [RuIV(bdpm)(pic)2(O)I(Cl)Ph]+ (H2bdpm = [2,2'-bipyridine]-6,6'-diylbis(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru-O(I) and O-I distances of 2.0451(39) and 1.9946(40) Å, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C-H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.