N-杂环卡宾官能化的铱磷烯配合物[Cp(NHC)Ir=PMes]：磷烯、亚胺基和卡宾配合物的比较

N-Heterocyclic carbene functionalized iridium phosphinidene complex [Cp(NHC)Ir=PMes]: comparison of phosphinidene, imido, and carbene complexes.

作者信息

Termaten Arjan T, Schakel Marius, Ehlers Andreas W, Lutz Martin, Spek Anthony L, Lammertsma Koop

机构信息

Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, NL-1081 HV, Amsterdam, The Netherlands.

出版信息

Chemistry. 2003 Aug 4;9(15):3577-82. doi: 10.1002/chem.200304744.

DOI:10.1002/chem.200304744

PMID:12898684

Abstract

The novel phosphinidene complex [Cp*(NHC)Ir=PMes*] (3; NHC=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) was prepared in high yield from [Cp*(NHC)IrCl(2)] (2) and [LiPHMes*].3 THF. It represents the first example of an NHC ligated transition metal phosphinidene complex. The X-ray crystal structure for 3 is also reported. DFT calculations on the N-heterocyclic carbene containing parent complexes [Cp(NHC)Ir=E] (E=PH, NH, CH(2)) show that the NHC ligand acts as good sigma-donor/weak pi-acceptor ligand and forms strong Ir-C(NHC) single bonds. The Ir=E double bonds result from strong triplet-triplet interactions between [Cp(NHC)Ir] and E.

摘要

新型磷烯配合物[Cp*(NHC)Ir=PMes*]（3；NHC = 1,3 - 二异丙基 - 4,5 - 二甲基咪唑 - 2 - 亚基）由[Cp*(NHC)IrCl₂]（2）和[LiPHMes*]·3THF高产率制备得到。它是NHC配位的过渡金属磷烯配合物的首个实例。还报道了3的X射线晶体结构。对含N - 杂环卡宾的母体配合物[Cp(NHC)Ir=E]（E = PH、NH、CH₂）的密度泛函理论计算表明，NHC配体作为良好的σ供体/弱π受体配体，并形成强的Ir - C(NHC)单键。Ir = E双键源于[Cp(NHC)Ir]与E之间强烈的三重态 - 三重态相互作用。