title: Correlations between (51)V solid-state NMR parameters and chemical structure of vanadium (V) complexes as models for related metalloproteins and catalysts.
abstract: The parameters describing the quadrupolar and CSA interactions of 51V solid-state MAS NMR investigations of model complexes mimicking vanadoenzymes as well as vanadium containing catalysts and enzyme complexes are interpreted with respect to the chemical structure. The interpretation is based on the data of 15 vanadium complexes including two new complexes with previously unpublished data and 13 complexes with data previously published by us. Correlations between the chemical structure and the 51V solid-state NMR data of this class of compounds have been established. Especially for the isotropic chemical shift delta(iso) and the chemical shift anisotropy delta(sigma), correlations with specific structural features like the coordination number of the vanadium atom, the number of coordinating nitrogens, the number of oxygen atoms and the chemical surrounding of the complex could be established for these compounds. Moreover, quantitative correlations between the solid-state NMR parameters and specific bond angles and bond lengths have been obtained. Our results can be of particular interest for future investigations concerning the structure and the mode of action of related vanadoenzymes and vanadate protein assemblies, including the use of vanadate adducts as transition state analogs for phosphate metabolizing systems.
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, D-07743 Jena, Germany.
authors.forename: Annika
authors.initials: A
authors.lastname: Fenn
authors.forename: Maria
authors.initials: M
authors.lastname: Wächtler
authors.forename: Torsten
authors.initials: T
authors.lastname: Gutmann
authors.forename: Hergen
authors.initials: H
authors.lastname: Breitzke
authors.forename: Axel
authors.initials: A
authors.lastname: Buchholz
authors.forename: Ines
authors.initials: I
authors.lastname: Lippold
authors.forename: Winfried
authors.initials: W
authors.lastname: Plass
authors.forename: Gerd
authors.initials: G
authors.lastname: Buntkowsky
mesh_terms: D055162:Biocatalysis; D040761:Biomimetic Materials / Q000737:chemistry / Q000378:metabolism; D020134:Catalytic Domain; D009682:Magnetic Resonance Spectroscopy; D008667:Metalloproteins / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D008968:Molecular Conformation; D010544:Peroxidases / Q000737:chemistry / Q000378:metabolism; D010710:Phosphates / Q000378:metabolism; D011789:Quantum Theory; D014638:Vanadates / Q000737:chemistry / Q000378:metabolism; D014639:Vanadium / Q000737:chemistry* / Q000378:metabolism
chemical_list: D008667:Metalloproteins; D010710:Phosphates; D014639:Vanadium; D014638:Vanadates; D010544:Peroxidases