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Mixed ruthenium-rhodium trinuclear complex (Ru/sub 2/Rh(. mu. /sub 3/-O)(. mu. -CH/sub 3/COO)/sub 6/(L)/sub 3/)/sup +/ (L = H/sub 2/O or pyridine)

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00255a018· OSTI ID:5737433
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The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, (Ru/sub 2/Rh(..mu../sub 3/-O)(..mu..-CH/sub 3/COO)/sub 6/(L)/sub 3/)/sup +/ (L = H/sub 2/O or pyridine (py)), are described. The mixed-metal structure was confirmed by the /sup 1/H and /sup 13/C NMR spectra (splitting of all the signals to a 1:2 intensity ratio) and the metal 3D electron signal intensities of the X-ray photoelectron spectra. The mixed-metal aqua and pyridine complexes exhibit an intense visible absorption peak at 576 nm (element of 2000 M/sup -1/ cm/sup -1/) and 590 (3980), respectively. Three reversible one-electron-redox waves are observed at +1.68, +0.79, and -0.78 V vs the Ag/Ag/sup +/ electrode for the pyridine complex in CH/sub 3/CN and are assigned to (Ru/sub 2/Rh)/sup 3+/2+/, (Ru/sub 2/Rh)/sup 2+/+/, and (Ru/sub 2/Rh)/sup +/0/, respectively. The /sup 1/H NMR spectrum of the aqua complex in CD/sub 3/OD changes slowly as the substitution of CD/sub 3/OD for the aqua ligands takes place, first-order rate constants being 6.0 x 10/sup -5/ (per Ru) and 1.2 x 10/sup -4/ s/sup -1/ at the ruthenium and the rhodium centers, respectively, at 21/sup 0/C.
Research Organization:
Tohoku Univ., Sendai, Japan
OSTI ID:
5737433
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:21; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AZINES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DEUTERIUM COMPOUNDS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDRATES
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PURIFICATION
PYRIDINES
REACTION KINETICS
RHODIUM COMPLEXES
RUTHENIUM COMPLEXES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES