Trimetallo derivatives of lacunary 9-tungstosilicate heteropolyanions. 2. Isotropic NMR shifts in pyridine-type ligands coordinated to the paramagnetic 9-tungsto-3-cuprio(II)silicate anion

Han Young Woo, Hyunsoo So, Michael T. Pope

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Abstract

1H NMR spectra of pyridine and α-, β-, and γ-picoline coordinated to the paramagnetic heteropolyanion [HmSiW9O37Cu3](10-m)- (SiW9Cu3) are reported. NMR lines are assigned to [HmSiW9O37Cu3(ptl)n] (10-m)- (n = 1, 2 or 3; m = 0, 1 or 2; ptl = pyridine-type ligands) on the basis of their pH and [SiW9Cu3]/[ptl] dependence. The isotropic NMR shifts come mainly from the contact shifts, which for some protons exceed 70% of those in analogous nickel complexes. The nuclear longitudinal relaxation times are 0.006, 0.06, and 0.1 s for α-, β-, and γ-H in pyridine coordinated to SiW9Cu3. The electronic correlation time calculated from the T1 values is in the order of 10-11 or 10-12 s, which is two or three orders of magnitude smaller than those of ordinary copper complexes. It is suggested that spin frustration causes rapid electronic relaxation in these complexes in which the three Cu2+ ions form an equilateral triangle.

Original languageEnglish
Pages (from-to)621-626
Number of pages6
JournalJournal of the American Chemical Society
Volume118
Issue number3
DOIs
Publication statusPublished - 1996 Jan 1
Externally publishedYes

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Silicates
Pyridine
Anions
Negative ions
Ligands
Nuclear magnetic resonance
Derivatives
Picolines
Frustration
Nickel
Relaxation time
Protons
Copper
Ions
pyridine

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Trimetallo derivatives of lacunary 9-tungstosilicate heteropolyanions. 2. Isotropic NMR shifts in pyridine-type ligands coordinated to the paramagnetic 9-tungsto-3-cuprio(II)silicate anion",
abstract = "1H NMR spectra of pyridine and α-, β-, and γ-picoline coordinated to the paramagnetic heteropolyanion [HmSiW9O37Cu3](10-m)- (SiW9Cu3) are reported. NMR lines are assigned to [HmSiW9O37Cu3(ptl)n] (10-m)- (n = 1, 2 or 3; m = 0, 1 or 2; ptl = pyridine-type ligands) on the basis of their pH and [SiW9Cu3]/[ptl] dependence. The isotropic NMR shifts come mainly from the contact shifts, which for some protons exceed 70{\%} of those in analogous nickel complexes. The nuclear longitudinal relaxation times are 0.006, 0.06, and 0.1 s for α-, β-, and γ-H in pyridine coordinated to SiW9Cu3. The electronic correlation time calculated from the T1 values is in the order of 10-11 or 10-12 s, which is two or three orders of magnitude smaller than those of ordinary copper complexes. It is suggested that spin frustration causes rapid electronic relaxation in these complexes in which the three Cu2+ ions form an equilateral triangle.",
author = "Woo, {Han Young} and Hyunsoo So and Pope, {Michael T.}",
year = "1996",
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T1 - Trimetallo derivatives of lacunary 9-tungstosilicate heteropolyanions. 2. Isotropic NMR shifts in pyridine-type ligands coordinated to the paramagnetic 9-tungsto-3-cuprio(II)silicate anion

AU - Woo, Han Young

AU - So, Hyunsoo

AU - Pope, Michael T.

PY - 1996/1/1

Y1 - 1996/1/1

N2 - 1H NMR spectra of pyridine and α-, β-, and γ-picoline coordinated to the paramagnetic heteropolyanion [HmSiW9O37Cu3](10-m)- (SiW9Cu3) are reported. NMR lines are assigned to [HmSiW9O37Cu3(ptl)n] (10-m)- (n = 1, 2 or 3; m = 0, 1 or 2; ptl = pyridine-type ligands) on the basis of their pH and [SiW9Cu3]/[ptl] dependence. The isotropic NMR shifts come mainly from the contact shifts, which for some protons exceed 70% of those in analogous nickel complexes. The nuclear longitudinal relaxation times are 0.006, 0.06, and 0.1 s for α-, β-, and γ-H in pyridine coordinated to SiW9Cu3. The electronic correlation time calculated from the T1 values is in the order of 10-11 or 10-12 s, which is two or three orders of magnitude smaller than those of ordinary copper complexes. It is suggested that spin frustration causes rapid electronic relaxation in these complexes in which the three Cu2+ ions form an equilateral triangle.

AB - 1H NMR spectra of pyridine and α-, β-, and γ-picoline coordinated to the paramagnetic heteropolyanion [HmSiW9O37Cu3](10-m)- (SiW9Cu3) are reported. NMR lines are assigned to [HmSiW9O37Cu3(ptl)n] (10-m)- (n = 1, 2 or 3; m = 0, 1 or 2; ptl = pyridine-type ligands) on the basis of their pH and [SiW9Cu3]/[ptl] dependence. The isotropic NMR shifts come mainly from the contact shifts, which for some protons exceed 70% of those in analogous nickel complexes. The nuclear longitudinal relaxation times are 0.006, 0.06, and 0.1 s for α-, β-, and γ-H in pyridine coordinated to SiW9Cu3. The electronic correlation time calculated from the T1 values is in the order of 10-11 or 10-12 s, which is two or three orders of magnitude smaller than those of ordinary copper complexes. It is suggested that spin frustration causes rapid electronic relaxation in these complexes in which the three Cu2+ ions form an equilateral triangle.

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