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N-Heterocyclic carbene functionalized iridium phosphinidene complex [Cp*(NHC)Ir=PMes*]: comparison of phosphinidene, imido, and carbene complexes. 2003
Arjan T Termaten, and
Marius Schakel, and
Andreas W Ehlers, and
Martin Lutz, and
Anthony L Spek, and
Koop Lammertsma
Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, NL-1081 HV, Amsterdam, The Netherlands.
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.
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