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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 14, Number 4
BKCSDE 14(4)
April 20, 1993 

 
Title
Isotropic NMR Shifts in Some Pyridine-Type Ligands Complexed with Paramagnetic Undecatungstocobalto(Ⅱ)silicate and Undecatungstonickelo(Ⅱ) silicate Anions. Identifications of Dumbbell-Shaped 4,4'-Bipyridyl Complexes
Author
Moonhee Ko, Gyung Ihm Rhyu, Hyunsoo So*
Keywords
Abstract
1H and 13C NMR spectra for pyridine, β-and γ -picoline, pyrazine, and 4,4'-bipyridyl complexed with paramagnetic undecatungstocobalto(Ⅱ)silicate and undecatungstonickelo(Ⅱ)silicate anions are reported. For these complexes the ligand exchange is slow on the NMR time scale and the pure resonance lines have been observed at room temperature. The isotropic shifts in nickel complexes can be interpreted in terms of contact shifts by σ-electron delocalization. Both contact and pseudocontact shifts contribute to the isotropic shifts in cobalt complexes. The contact shifts, which are obtained by subtracting the pseudocontact shifts from the isotropic shifts, require both σ-and π-electron delocalization from the cobalt ion. Slow ligand exchange has also allowed us to identify the species formed when bidentate ligands react with the heteropolyanions. Pyrazine forms a 1 : 1 complex, while 4,4'-bipyridyl forms both 1 : 1 and dumbbell-shaped 1 : 2 complexes.
Page
500 - 506
Full Text
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