期刊
ORGANOMETALLICS
卷 27, 期 17, 页码 4484-4493出版社
AMER CHEMICAL SOC
DOI: 10.1021/om800404q
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资金
- School of Physical and Mathematical Sciences, Nanyang Technological University
- Johnson Matthey Co
A series of rhodium and iridium complexes of quinoline-tethered hemilabile N-heterocyclic carbenes ((NHCN)-N-boolean AND) have been synthesized via either deprotonation of imidazolium salts or silver transmetalation. Deprotonation of imidazolium ions by (BuOK)-Bu-1 in the presence of [Rh(COD)Cl](2) (COD = 1,5-cyclooctadiene) afforded both chelating [Rh(COD)((NHCN)-N-boolean AND)](+) and monodentate [Rh(COD)(NHC)(2)](+) complexes, while only the chelating carbene complexes were obtained for the iridium analogues. Silver transmetalation of this type of carbene to [M(COD)Cl](2) (M = Rh, Ir) consistently afforded M(NHC) (COD)Cl, maintaining the metal chloride and pendant quinoline entity. Carbene transmetalation to (Cp*IrCl2)(2) gave an equilibrium mixture of neutral Cp*Ir(NHC)Cl-2 and ionic [Cp*Ir((NHCN)-N-boolean AND)Cl]Cl. All these rhodium and iridium cyclooctadiene complexes can undergo one-electron oxidation in cyclic voltammetry. The variable-scan-rate cyclic voltammetry experiments indicate that these compounds undergo slow heterogeneous electron transfer and that the oxidized forms are relatively short-lived. A neutral Rh(COD)(NHC)Cl complex proved to be active in catalyzing the [3 + 2] cycloaddition reactions of diphenylcyclopropenone and internal alkynes. Crystal structures of metal complexes in each category have been reported.
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