Isomerization dynamics and control of the eta2/N equilibrium for pyridine complexes.
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.
Delafuente
David A
DA
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA.
Kosturko
George W
GW
Graham
Peter M
PM
Harman
W Hill
WH
Myers
William H
WH
Surendranath
Yogesh
Y
Klet
Rachel C
RC
Welch
Kevin D
KD
Trindle
Carl O
CO
Sabat
Michal
M
Harman
W Dean
WD
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*
D009942:Organometallic Compounds; D011725:Pyridines; D014414:Tungsten