Linear Free Energy Relationships Associated with Hydride Transfer From (6,6'-R2-bpy)Re(CO)3H: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere

• Published in: Inorganic chemistry 2024-10, Vol.63 (41), p.19396
• Main Authors: Elsby, Matthew R, Kumar, Abhishek, Daniels, Lee M, Ertem, Mehmed Z, Hazari, Nilay, Mercado, Brandon Q, Paulus, Alexandra H
• Format: Article
• Language: English
• ISSN: 1520-510X; 1520-510X
• DOI: 10.1021/acs.inorgchem.4c03365

Six rhenium hydride complexes, [(6,6'-R2-bpy)Re(CO)3H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO2 to form rhenium formate complexes of the type [(6,6'-R2-bpy)Re(CO)3{OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me2-bpy)Re(CO)3H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO2 insertion into complexes of the type [(6,6'-R2-bpy)Re(CO)3H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R2-bpy)Re(CO)3H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO2 insertion and the calculated thermodynamic hydricities for [(6,6'-R2-bpy)Re(CO)3H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO2 insertion into complexes of the type [(4,4'-R2-bpy)Re(CO)3H]. At a given thermodynamic hydricity, CO2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe)2-bpy ligand could in principle stabilize the transition state for CO2 insertion via hydrogen bonding. This work shows that if only the rate of CO2 insertion into [(6,6'-(NHMe)2-bpy)Re(CO)3H] is compared to [(4,4'-R2-bpy)Re(CO)3H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.Six rhenium hydride complexes, [(6,6'-R2-bpy)Re(CO)3H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO2 to form rhenium formate complexes of the type [(6,6'-R2-bpy)Re(CO)3{OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me2-bpy)Re(CO)3H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO2 insertion into complexes of the type [(6,6'-R2-bpy)Re(CO)3H] were measured exp