title: Nickel pincer model of the active site of lactate racemase involves ligand participation in hydride transfer.
abstract: Lactate racemase is the first enzyme known to possess a metal pincer active site. The enzyme interconverts d- and l-lactic acid, which is important for the assembly of cell walls in many microorganisms. Here, we report a synthetic model of the active site of lactate racemase, which features a pyridinium-based SCS pincer ligand framework bound to nickel. The model complex mediates the dehydrogenation of alcohols, a reaction relevant to lactate racemization. Experimental and computational data indicate ligand participation in the dehydrogenation reaction.
authors.affiliation: Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland.
authors.forename: Tao
authors.initials: T
authors.lastname: Xu
authors.affiliation: Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland.|Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland.
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Wodrich
authors.affiliation: Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland.
authors.forename: Rosario
authors.initials: R
authors.lastname: Scopelliti
authors.affiliation: Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland.
authors.forename: Clemence
authors.initials: C
authors.lastname: Corminboeuf
authors.affiliation: Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland; xile.hu@epfl.ch.
authors.forename: Xile
authors.identifier: 0000-0001-8335-1196
authors.initials: X
authors.lastname: Hu
mesh_terms: D000438:Alcohols / Q000737:chemistry; D032701:Biomimetics; D020134:Catalytic Domain; D008024:Ligands; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000737:chemistry; D019998:Racemases and Epimerases / Q000737:chemistry*
chemical_list: D000438:Alcohols; D008024:Ligands; D011726:Pyridinium Compounds; D009532:Nickel; D019998:Racemases and Epimerases; C021498:lactate racemase
keywords: biomimetic chemistry; hydride transfer; lactate racemase; nickel; pincer ligands