An EXAFS spectroscopic study of solvates of copper(I) and copper(II) in acetonitrile, dimethyl sulfoxide, pyridine, and tetrahydrothiophene solutions and a large-angle X-ray scattering study of the copper(II) acetonitrile solvate in solution

Journal Article · Wed May 26 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00063a049· OSTI ID:5786007

Persson, I ^[1]; Penner-Hahn, J E ^[2]; Hodgson, K O ^[3]

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1. Swedish Univ. of Agricultural Sciences, Uppsala (Sweden)
2. Univ. of Michigan, Ann Arbor (United States) Stanford Univ., CA (United States)
3. Univ. of Michigan, Ann Arbor (United States)

X-ray absorption edge and EXAFS spectra of the acetonitrile, dimethyl sulfoxide, pyridine and tetrahydrothiophene solvated copper(I) ions and the acetonitrile and dimethyl sulfoxide solvated copper(II) ions have been measured in solution. Analysis reveals that the copper(I) solvates are most probably tetrahedral, and the following Cu-solvate bond distances have been found: Cu-N = 1.99(2) [angstrom] in acetonitrile, Cu-O = 2.09(4) [angstrom] in dimethyl sulfoxide, Cu-N = 2.06(1) [angstrom] in pyridine, and Cu-S = 2.30(1) [angstrom] in tetrahydrothiophene. The copper(II) solvates are most probably Jahn-Teller distorted octahedrons, and the following equatorial Cu-solvate bond distances have been found: Cu-N = 1.99(1) [angstrom] in acetonitrile, and Cu-O = 1.98(1) [angstrom] in dimethyl sulfoxide. An 1.0 M solution of copper(II) trifluoromethanesulfonate in acetonitrile has been studied by means of the large-angle X-ray scattering technique, and the following Cu-N and Cu-C distances have been found for the Cu(CH[sub 3]CN)[sub 4][sup 2][sup +] complex: 1.99(1) and 3.12(1) [angstrom], respectively. No solvate molecules in the axial positions could however be seen by any of the technique used. The structure of the tetraaquacopper(I) ion has been assumed to be tetrahedral, and from a correlation between the difference in bond length between the copper(I) and copper(II) solvates and the disproportionation constants of copper(I) in the solvent, the Cu-O bond distance is predicted to be approximately 0.14 [angstrom] longer than the equatorial Cu-O distances in the Jahn-Teller distorted hexaaquacopper(II) complex, thus about 2.13 [angstrom].

• OSTI ID: 5786007
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:11; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER COMPLEXES
MOLECULAR STRUCTURE
ABSORPTION SPECTROSCOPY
ACETONITRILE
BOND LENGTHS
CATIONS
DMSO
JAHN-TELLER EFFECT
POLYCYCLIC SULFUR HETEROCYCLES
PYRIDINE
SOLVATION
X-RAY SPECTROSCOPY
AZINES
CHARGED PARTICLES
COMPLEXES
DIMENSIONS
HETEROCYCLIC COMPOUNDS
IONS
LENGTH
NITRILES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PYRIDINES
SPECTROSCOPY
SULFOXIDES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties