Sung Simon, Young Rowan D
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543.
Dalton Trans. 2017 Nov 14;46(44):15407-15414. doi: 10.1039/c7dt03690f.
We report the facile generation of Ir PCP pincer systems. These systems are accessed from the reaction between [IrCl(COD)] and a bis(diphenyl)phenylene P(OH)P proligand (1) with concomitant dehydration, followed by salt metathesis/ligand exchange in the case of cationic examples. In contrast to previously reported double C-H activation synthetic strategies to access similar complexes, accessing Ir PCP complexes through dehydration proceeds rapidly at room temperature and provides the first example of the incorporation of phosphino aryl substituents. The generated complexes are shown to possess the ability to activate inert C-H bonds and partake in ligand cooperativity. Mechanistic evidence suggests that divergent C-H and O-H activation pathways of ligand 1 ultimately lead to the same Ir PCP product (2). It is hoped that the stability and synthetic accessibility of these complexes will encourage their increased use in catalyst surveys.
我们报道了铱磷环戊二烯钳形体系的简便合成方法。这些体系是通过[IrCl(COD)]与双(二苯基)亚苯基P(OH)P前体配体(1)反应并伴随脱水而得到的,对于阳离子型示例,随后进行盐复分解/配体交换。与先前报道的通过双C-H活化合成策略来制备类似配合物不同,通过脱水制备铱磷环戊二烯配合物在室温下即可快速进行,并提供了膦基芳基取代基引入的首个实例。所生成的配合物显示出能够活化惰性C-H键并参与配体协同作用。机理证据表明,配体1不同的C-H和O-H活化途径最终导致相同的铱磷环戊二烯产物(2)。希望这些配合物的稳定性和合成可及性将促使它们在催化剂研究中得到更多应用。