Bio-Inspired Transition Metal-Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory

• Published in: Chemistry : a European journal Vol. 21; no. 7; pp. 2821 - 2834
• Main Authors: McSkimming, Alex, Chan, Bun, Bhadbhade, Mohan M., Ball, Graham E., Colbran, Stephen B.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 09-02-2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Barriers; biomimetic systems; Catalysis; Catalysts; Chemistry; density functional calculations; Hydrides; Hydrogenation; Imines; Iridium; ligand design; Models, Molecular; Molecular Structure; Oxidation-Reduction; Theory; transfer hydrogenation; Transition Elements - chemistry; Yeast; biomimetic systems; hydrides; ligand design; density functional calculations; transfer hydrogenation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201405129

Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI+) organic hydride‐acceptor domain has been coupled with a 1,10‐phenanthroline (phen) metal‐binding domain to afford a novel multifunctional ligand (LBI+) with hydride‐carrier capacity (LBI++H−⇌LBIH). Complexes of the type [Cp*M(LBI)Cl][PF6]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the IrIII congener, X‐ray crystallography. [Cp*Rh(LBI)Cl][PF6]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(LBI)Cl][PF6] and [Cp*M(phen)Cl][PF6] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate‐driven RhH formation (90 kJ mol−1 free‐energy barrier), transfer of hydride between the Rh and BI+ centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back‐transfer of hydride from the BIH organic hydride donor to the Rh‐activated imine substrate (89 kJ mol−1 barrier), and exergonic protonation of the metal‐bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.
Inspired by the yeast alcohol dehydrogenase‐catalyzed reduction of acetaldehyde to ethanol, a new catalyst for transfer hydrogenation of imines, based on a multifunctional ligand incorporating a benzimidazolium organic hydride‐acceptor domain and a 1,10‐phenanthroline metal‐binding domain, has been designed and realised. Theory and experiment suggest hydride transfer from an organic hydride donor is a key step in both catalyses.