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Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory
Author(s) -
McSkimming Alex,
Chan Bun,
Bhadbhade Mohan M.,
Ball Graham E.,
Colbran Stephen B.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405129
Subject(s) - chemistry , hydride , catalysis , formate , protonation , transfer hydrogenation , inorganic chemistry , photochemistry , medicinal chemistry , metal , organic chemistry , ruthenium , ion
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 ( L BI + ) with hydride‐carrier capacity ( L BI + +H − ⇌ L BI H). Complexes of the type [Cp*M( L BI )Cl][PF 6 ] 2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir III congener, X‐ray crystallography. [Cp*Rh( L BI )Cl][PF 6 ] 2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir( L BI )Cl][PF 6 ] and [Cp*M(phen)Cl][PF 6 ] (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 RhH 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.