title: Isomerization dynamics and control of the eta2/N equilibrium for pyridine complexes.
abstract: A series of pyridine complexes are prepared of the general form TpW(NO)(PMe3)(pyr) where pyr is either pyridine or a substituted pyridine. Depending on substitution pattern, the pyridine can be either N- or eta2-coordinated, and the role of the pyridine substituents and metal oxidation state in determining this equilibrium is explored. For eta2-pyridine complexes, the substituent pattern and solubility characteristics also determine the ratio of coordination diastereomers. Rates of both intra- and interfacial linkage isomerizations are explored along with the pyridine rotational barrier. This study is supported by DFT calculations and X-ray data and includes characterization of both eta2-pyridine and eta2-pyridinium complexes.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA.
authors.forename: David A
authors.initials: DA
authors.lastname: Delafuente
authors.forename: George W
authors.initials: GW
authors.lastname: Kosturko
authors.forename: Peter M
authors.initials: PM
authors.lastname: Graham
authors.forename: W Hill
authors.initials: WH
authors.lastname: Harman
authors.forename: William H
authors.initials: WH
authors.lastname: Myers
authors.forename: Yogesh
authors.initials: Y
authors.lastname: Surendranath
authors.forename: Rachel C
authors.initials: RC
authors.lastname: Klet
authors.forename: Kevin D
authors.initials: KD
authors.lastname: Welch
authors.forename: Carl O
authors.initials: CO
authors.lastname: Trindle
authors.forename: Michal
authors.initials: M
authors.lastname: Sabat
authors.forename: W Dean
authors.initials: WD
authors.lastname: Harman
mesh_terms: D018360:Crystallography, X-Ray; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism; D014414:Tungsten / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D011725:Pyridines; D014414:Tungsten