title: Which functional groups of the molybdopterin ligand should be considered when modeling the active sites of the molybdenum and tungsten cofactors? A density functional theory study.
abstract: A density functional theory study of the influence of the various functional groups of the molybdopterin ligand on electronic and geometric properties of active-site models for the molybdenum and tungsten cofactors has been undertaken. We used analogous molybdenum and tungsten complexes with increasingly accurate representation of the molybdopterin ligands and compared bond lengths, angles, charge distribution, composition of the binding orbitals, as well as the redox potentials in relation to each other. On the basis of our findings, we suggest using ligand systems including the pyrane and the pyrazine rings, besides the dithiolene function, to obtain sufficiently reliable computational, but also synthetic, models for the molybdenum and tungsten cofactors, whereas the second ring of the pterin might be neglected for efficiency reasons.
authors.affiliation: Department of Theoretical Chemistry, Chemical Center, Lund University, 124, 22100 Lund, Sweden.
authors.forename: Ulf
authors.initials: U
authors.lastname: Ryde
authors.forename: Carola
authors.initials: C
authors.lastname: Schulzke
authors.forename: Kerstin
authors.initials: K
authors.lastname: Starke
mesh_terms: D002384:Catalysis; D020134:Catalytic Domain; D003067:Coenzymes / Q000737:chemistry*; D019295:Computational Biology; D008024:Ligands; D008667:Metalloproteins / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D000090006:Molybdenum Cofactors; D009942:Organometallic Compounds / Q000737:chemistry*; D011621:Pteridines / Q000737:chemistry*; D011622:Pterins / Q000737:chemistry*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D003067:Coenzymes; D008024:Ligands; D008667:Metalloproteins; D008982:Molybdenum; D000090006:Molybdenum Cofactors; D009942:Organometallic Compounds; D011621:Pteridines; D011622:Pterins; D014414:Tungsten; C080020:tungsten cofactor; C022261:molybdopterin