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Synthesis and characterization of tetraamminerruthenium(II) bound to the bridging ligand 2,3-bis(2-pyridyl)pyrazine (dpp)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00295a026· OSTI ID:6181424
The synthesis, electronic absorption spectra, electrochemistry, /sup 13/C NMR spectra, and photochemistry of (NH/sub 3/)/sub 4/Ru(dpp)/sup 2 +/ and (NH/sub 3/)/sub 4/Ru(dpp)Ru(NH/sub 3/)/sub 4//sup 4 +/ are reported. The aqueous visible electronic absorption spectra show intense MLCT transitions occur at 454 and 545 nm for the monometallic complex and at 558 nm for the bimetallic complex. Cyclic voltammograms of (NH/sub 3/)/sub 4/Ru(dpp)/sup 2 +/ in CH/sub 3/CN/0.1 M TBAP show a reversible couple at E/sub 1/2/ = +1.01 V, and voltammograms of (NH/sub 3/)/sub 4/Ru(dpp)Ru(NH/sub 3/)/sub 4//sup 4 +/ show two couples at E/sub 1/2/(I) = +0.90 V and E/sub 1/2/(2) = +1.29 V vs NHE. The decrease in E/sub 1/2/(1) for the bimetallic complex vs E/sub 1/2/ for the monometallic complex is interpreted as being due to the addition of sigma-donating NH/sub 3/ ligands via the additional ruthenium center. The ..delta..E/sub 1/2/(2-1) value of 390 mV for the bimetallic complex indicates excellent metal-metal communication through the bridging ligand. Extended irradiation of the MLCT transitions of both complexes yields NH/sub 3/ release with wavelength-dependent /Phi//sub max/ < 3 x 10/sup -4/ for reactant loss. 22 references, 3 figures, 3 tables.
Research Organization:
Univ. of Colorado, Colorado Springs (USA)
OSTI ID:
6181424
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:22; ISSN INOCA
Country of Publication:
United States
Language:
English