Add time:07/21/2019         Source:sciencedirect.com

Pentacarbonylbromorhenium(I) reacted with 2,6-bis(benzimidazol-2′-yl)pyridine (bbip), 2,6-bis(1′-methylbenzimidazol-2′-yl)pyridine (bmbip), 2,6-bis(5′,6′-dimethylbenzimidazol-2′-yl)pyridine (bdmbip), and 2,6-bis(1′,5′,6′-trimethylbenzimidazol-2′-yl)pyridine (btmbip) to form stable octahedral complexes of type fac-[ [ReBr(CO)3L] (L = bbip, bmbip, bdmbip or btmbip in which L is acting as a bidentate chelate ligand. At above-ambient temperatures in solution the complexes are fluxional with the nitrogen ligand oscillating between equivalent bidentate bonding modes. Rates and activation energies for these fluxions have been investigated by NMR methods. At low temperatures rotation of the uncoordinated nenzimidazolyl unit is restricted and for fac-[ReBr(CO)3(btmbip)] in CD2Cl2 solution, two preferred rotamers exist in 89:11% relative abundances. A rotational energy barrier has been estimated. The X-ray crystal structure of fac-[ReBr(CO)3)(btmbip)] confirms the bidentate chelate bonding of btmbip with a NReN angle of 74.2°. The pendant benzimidazole unit is inclined at an angle of 60.7° to the pyridine ring.

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