Detailed Spectroscopic, Thermodynamic, and Kinetic Characterization of Nickel(II) Complexes with 2,2‘-Bipyridine and 1,10-Phenanthroline Attained via Equilibrium-Restricted Factor Analysis

Douglas A. Vander Griend,* Daniel Kwabena Bediako, Michael J. DeVries, Nathan A. DeJong, and Lee P. Heeringa
Department of Chemistry and Biochemistry, Calvin College, 1726 Knollcrest Circle SE, Grand Rapids, Michigan 49546-4403
Inorg. Chem., 2008, 47 (2), pp 656–662
DOI: 10.1021/ic700553d
Publication Date (Web): December 21, 2007
Copyright © 2008 American Chemical Society
*

 To whom correspondence should be addressed. E-mail:  dvg@calvin.edu.

Abstract

Abstract Image

The molar absorptivity curves of the mono and bis nickel(II) complexes of 2,2‘-bipyridine and 1,10-phenanthroline have been deduced from the composite absorbance data of a series of equilibrium solutions in methanol using equilibrium-restricted factor analysis, a technique for extracting spectral and thermodynamic information for component species involved in solution equilibria. The solutions achieve equilibrium slowly (t1/2 ≈ 100 min) as the amounts of the tris and methanolato complexes are initially in excess. The relative formation constants at 293 K have been determined with a high degree of accuracy, especially for the bipyridine complexes:  log(K1/K2) = 0.340(4) and log(K2/K3) = 1.091(6). Solubility limitations compromised the accuracy of the thermodynamic results for the phenanthroline complexes.

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History

  • Published In Issue January 21, 2008
  • Received March 23, 2007

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