title: Toward functional type III [Fe]-hydrogenase biomimics for H2 activation: insights from computation.
abstract: The chemistry of [Fe]-hydrogenase has attracted significant interest due to its ability to activate molecular hydrogen. The intriguing properties of this enzyme have prompted the synthesis of numerous small molecule mimics aimed at activating H2. Despite considerable effort, a majority of these compounds remain nonfunctional for hydrogenation reactions. By using a recently synthesized model as an entry point, seven biomimetic complexes have been examined through DFT computations to probe the influence of ligand environment on the ability of a mimic to bind and split H2. One mimic, featuring a bidentate diphosphine group incorporating an internal nitrogen base, was found to have particularly attractive energetics, prompting a study of the role played by the proton/hydride acceptor necessary to complete the catalytic cycle. Computations revealed an experimentally accessible energetic pathway involving a benzaldehyde proton/hydride acceptor and the most promising catalyst.
authors: Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland).
authors: Kevin A
authors: KA
authors: Murray
authors: Matthew D
authors: MD
authors: Wodrich
authors: Xile
authors: X
authors: Hu
authors: Clémence
authors: C
authors: Corminboeuf
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry*; D032701:Biomimetics; D002384:Catalysis; D039301:Computers, Molecular; D006864:Hydrogenase / Q000737:chemistry*; D006865:Hydrogenation; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D011522:Protons; D011789:Quantum Theory
chemical_list: D001547:Benzaldehydes; D007506:Iron-Sulfur Proteins; D008024:Ligands; D011522:Protons; C118830:iron hydrogenase; D006864:Hydrogenase
keywords: biomimetic chemistry; density functional calculations; enzyme models; hydrogenase; ligand effects