A series of cationic rhodium(I) and iridium(I) complexes of the type [M(L∩L)(C2)]BArF24 (where M = Rh or Ir, L∩L = bis(pyrazol-1-yl)methane (bpm), bis(N-methylimidazol-2-yl)methane (bim) or 1-(2-(diphenylphosphino)ethyl)-3,5-diphenylpyrazole (Ph2PyP), C2 = 1,5-cyclooctadiene (COD) or (CO)2 and BArF24 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) were synthesised in good yields. The solid-state structure of a number of complexes, including [Ir(Ph2PyP)(COD)]BArF24, [Ir(bpm)(COD)]BArF24 and [Ir(bim)(COD)]BArF24 was determined using X-ray crystallography. The efficiency of the complexes as catalysts for the intramolecular hydroamination of 4-phenyl-3-butyn-1-amine, 4-pentyn-1-amine and 2-(2-phenylethynyl)aniline was established. The incorporation of the BArF24− counter-ion in the Rh(I) and Ir(I) complexes was found to significantly improve the catalytic activity of the complexes, compared to the analogous Rh(I) and Ir(I) complexes containing BPh4− as the counter-ion. Excellent conversions were achieved for the cyclisation of 2-(2-phenylethynyl)aniline to 2-phenylindole using [Rh(bpm)(CO)2]BArF24 as a catalyst. The use of a microwave reactor for enhancing the catalysed reactions was also investigated.
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