A new type of dianionic Ir(III) CCC pincer complexes (SNHC-Ir, 1a-1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C- H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange, and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory (DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.

通过开发一步法成功设计并合成了一种新型的阴离子双价Ir（III）CCC钳形配合物（SNHC-Ir，1a - 1c），该方法涉及Ir（I）与NHC的初始配位和随后的金属化sp2C-H双键。该方法相对于通过使用强配位配体或碳阴离子交换所报道的方法而言非常有用，并且将提供有机金属合成的另一种有效模板。实验和密度泛函理论（DFT）的计算结果表明，螺环骨架是这些复合物的容易形成和稳定的有利因素。初步调查表明，氯化物1b 可以很好地催化苯乙烯衍生物的均相和杂相加成以及远距离的烯烃异构化，这代表了双阴离子CCC钳形配合物的首次催化应用。