2,2′:6′,2″-Terpyridine (terpy) acting as a fluxional bidentate ligand. Part 2. Rhenium carbonyl halide complexes, fac-[ReX(CO)3(terpy)](X = Cl, Br or I): NMR studies of their solution dynamics, synthesis of cis-[ReBr(CO)2(terpy)] and the crystal structure of [ReBr(CO)3(terpy)]

Abstract

Under mild conditions pentacarbonylhalogenorhenium(I) complexes react with 2,2′:6′,2″-terpyridine (terpy) to form stable octahedral tricarbonyl complexes fac-[ReX(CO)₃(terpy)](X = Cl, Br or I) in which the terpyridine acts as a bidentate chelate ligand. Under more severe reaction conditions fac-[ReBr(CO)₃(terpy)] can be converted to cis-[ReBr(CO)₂(terpy)]. In solution the tricarbonyl complexes are fluxional with the terpyridine oscillating between equivalent bidentate bonding modes. At low temperatures rotation of the unco-ordinated pyridine ring is restricted and in CD₂Cl₂ solution two preferred rotamers exist in approximately equal abundances. Rotational energy barriers have been estimated for the X = Cl and I complexes. The X-ray crystal structure of fac-[ReBr(CO)₃(terpy)] confirms the bidentate chelate bonding of terpy with a N–Re–N angle of 74.3°. The pendant pyridine ring is inclined at an angle of 52.9° to the adjacent co-ordinated ring and the unco-ordinated nitrogen is directed towards the axial carbonyl and trans to Br.