Carbene complexes. Part VI. Complexes from imidoyl chloride and rhodium(I) precursors, and the crystal and molecular structure of carbonyltri-iodo-[α-(N-methyl-α-methyliminobenzylamino)benzylidene-N,C]rhodium, I3(OC)Rh–CPh(NMe)CPh:NMe

Abstract

The reaction of an imidoyl chloride R¹C(Cl):NR² with the Rh^I complex [Rh(CO)₂Cl]₂ in the rigorous absence of hydrogen chloride affords the Rh^III carbene chelate Cl₃(OC)[graphic omitted]R². The chloride ligands are replaceable by Br^– or I^–, and the chelate bridge is cleaved by reaction with a tertiary phosphine. A single-crystal X-ray analysis of (IV) I₃(OC)[graphic omitted]Me by the heavy-atom method has been refined to R 0·047 for 2400 independent terms measured on a diffractometer: the complex has an approximately octahedral Rh environment, with Rh–C(carb) 1·968(13), C(carb)–N 1·328(16), Rh–N 2·047(9), Rh–I 2·662(4)—2·774(4), and Rh–C(O) 1·892(14)Å. Crystals are monoclinic, a= 10·83(1), b= 17·24(2), c= 11·52(1)Å, β= 97·3(2)°, Z= 4, space group P2₁/n.