Skip to main content
Journal cover image

Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation.

Publication ,  Journal Article
Szczepankiewicz, SH; Ippolito, CM; Santora, BP; Van De Ven, TJ; Ippolito, GA; Fronckowiak, L; Wiatrowski, F; Power, T; Kozik, M
Published in: Inorg Chem
August 24, 1998

Tetraheptylammonium salts of various transition-metal-substituted heteropolyanions with alpha-Keggin ([XW(11)O(39)M](n)()(-)), alpha-Wells-Dawson ([P(2)W(17)O(61)M](m)(-)), and Weakley and Finke structures ([P(2)W(18)O(68)Co(4)](10)(-)) were investigated with respect to their reactivity with CO(2) in nonpolar solvents. It was found that copper(II)- and manganese(III)-substituted heteropolyanions do not react with CO(2). Germano- and silicotungstates with the alpha-Keggin structure do form complexes with CO(2) when substituted with Co(II), Ni(II), and Mn(II). In contrast, boro- and phosphotungstates substituted with Co(II), Ni(II), and Mn(II) are unreactive. The alpha(2) isomers of Wells-Dawson phosphotungstates show reactivity similar to that of alpha-Keggin silicotungstates-i.e., Co(II), Ni(II), and Mn(II) derivatives do react with CO(2). On the other hand, the alpha(1) isomer of the Co(II)-substituted Wells-Dawson anion does not react with CO(2), and neither does the Weakley and Finke cobaltotungstate. When reactions do occur, they are completely reversible. An excess of water decomposes the complexes. Traces of water are, however, necessary for the reactions to take place. The CO(2) adducts were characterized by UV/vis, IR, and (13)C NMR. The IR data could be explained as originating either from CO(2) complexes with a direct eta(1) metal-carbon bond or from bicarbonato complexes. IR spectra with isotopically enriched (13)CO(2) and C(18)O(2) support the presence of a eta(1) metal-carbon bond. The (13)C NMR spectra indicate the presence of two different kinds of paramagnetic CO(2) complexes after the reaction of alpha-[SiW(11)O(39)Co](6)(-) with CO(2) (chemical shifts 792 and 596 ppm at 26 degrees C). The variable-temperature experiments are consistent with the chemical exchange between these two species. UV/vis, IR, and NMR studies in the presence of controlled amounts of water or ethanol suggest the existence of H-bonding in the CO(2) complexes, similar to that reported in the past for complexes between heteropolyanions and dioxygen.

Duke Scholars

Published In

Inorg Chem

DOI

EISSN

1520-510X

Publication Date

August 24, 1998

Volume

37

Issue

17

Start / End Page

4344 / 4352

Location

United States

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Szczepankiewicz, S. H., Ippolito, C. M., Santora, B. P., Van De Ven, T. J., Ippolito, G. A., Fronckowiak, L., … Kozik, M. (1998). Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation. Inorg Chem, 37(17), 4344–4352. https://doi.org/10.1021/ic980162k
Szczepankiewicz, Steven H., Calogero M. Ippolito, Brian P. Santora, Thomas J. Van De Ven, Giuseppe A. Ippolito, Louise Fronckowiak, Fred Wiatrowski, Tom Power, and Mariusz Kozik. “Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation.Inorg Chem 37, no. 17 (August 24, 1998): 4344–52. https://doi.org/10.1021/ic980162k.
Szczepankiewicz SH, Ippolito CM, Santora BP, Van De Ven TJ, Ippolito GA, Fronckowiak L, et al. Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation. Inorg Chem. 1998 Aug 24;37(17):4344–52.
Szczepankiewicz, Steven H., et al. “Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation.Inorg Chem, vol. 37, no. 17, Aug. 1998, pp. 4344–52. Pubmed, doi:10.1021/ic980162k.
Szczepankiewicz SH, Ippolito CM, Santora BP, Van De Ven TJ, Ippolito GA, Fronckowiak L, Wiatrowski F, Power T, Kozik M. Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation. Inorg Chem. 1998 Aug 24;37(17):4344–4352.
Journal cover image

Published In

Inorg Chem

DOI

EISSN

1520-510X

Publication Date

August 24, 1998

Volume

37

Issue

17

Start / End Page

4344 / 4352

Location

United States

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry