Synthesis and characterization of tetraamminerruthenium(II) bound to the bridging ligand 2,3-bis(2-pyridyl)pyrazine (dpp)
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), Vol. 27:22
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIA
SYNTHESIS
PYRAZINES
PYRIDYL RADICALS
QUATERNARY COMPOUNDS
RUTHENIUM COMPLEXES
CARBON 13
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
NMR SPECTRA
PHOTOCHEMISTRY
AMINES
AMMONIUM COMPOUNDS
AZINES
CARBON ISOTOPES
CHEMISTRY
COMPLEXES
DATA
EVEN-ODD NUCLEI
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADICALS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation