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

Elsby, Matthew R.; Kumar, Abhishek; Daniels, Lee M.; Ertem, Mehmed Z.; Hazari, Nilay; Mercado, Brandon Q.; Paulus, Alexandra H.

doi:10.1021/acs.inorgchem.4c03365

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

Journal Article · Mon Sep 30 00:00:00 EDT 2024 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.4c03365· OSTI ID:2477952

Elsby, Matthew R. ^[1]; Kumar, Abhishek ^[1]; Daniels, Lee M. ^[2]; ^[3]; ^[1]; Mercado, Brandon Q. ^[1]; Paulus, Alexandra H. ^[1]

Yale Univ., New Haven, CT (United States)
Rigaku Oxford Diffraction, The Woodlands, TX (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2477952

Report Number(s):: BNL--226354-2024-JAAM

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 41 Vol. 63; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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