Termaten Arjan T, Schakel Marius, Ehlers Andreas W, Lutz Martin, Spek Anthony L, Lammertsma Koop
Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, NL-1081 HV, Amsterdam, The Netherlands.
Chemistry. 2003 Aug 4;9(15):3577-82. doi: 10.1002/chem.200304744.
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.
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。
