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Updated: May 23, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Metal-Ligand Cooperativity via Π-Π Interactions Supporting Outer-Sphere Hydride Transfer
Ashu Singh1, Vishal Jaiswal1, Shilpi Misra2
1Department of Chemistry, Indian Institute of Technology Indore, Simrol, Indore, 453552, India.
None:
A set of phosphine-free Ru(II)-CNC pincer complexes with benzimidazolylidene-based CNC-ligands has been synthesized and characterized, which show excellent catalytic activity toward α-alkylation of ketones using primary alcohols. DFT investigations revealed that these seemingly nonbifunctional complexes can operate via inner- and outer-sphere mechanisms for the alcohol dehydrogenation step; however, the outer-sphere path is favored for the subsequent steps. The outer-sphere path is found to be supported by π-π interaction between the extended aromatic ring system of the benzimidazolylidene-based CNC-ligand and aromatic rings of the substrates in a new, unprecedented case of metal-ligand cooperativity.
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