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N-Heterocyclic Carbene Functionalized Iridium Phosphinidene Complex [Cp*(NHC)IrPMes*]: Comparison of Phosphinidene, Imido, and Carbene Complexes

✍ Scribed by Arjan T. Termaten; Marius Schakel; Andreas W. Ehlers; Martin Lutz; Anthony L. Spek; Koop Lammertsma

Publisher
John Wiley and Sons
Year
2003
Tongue
English
Weight
153 KB
Volume
9
Category
Article
ISSN
0947-6539

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✦ Synopsis

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 σ‐donor/weak π‐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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## Abstract A series of hydroxyalkyl‐functionalized imidazolium salts have been coordinated to Rh and Ir to afford the corresponding MCp\*–(NHC) (Cp\*=pentamethylcyclopentadienyl) complexes. The reactivity of the new complexes has been studied with special attention to the transformations that deal