Photoracemization/substitution of optically active rhodium(III) complexes, cis-L-Rh(en)/sub 2/(OH)X/sup n+/
The photochemistry of cis-L-Rh(en)/sub 2/(H/sub 2/O)(OH)/sup 2 +/ and cis-L-Rh(en)/sub 2/(OH)/sub 2//sup +/ in aqueous solution is reported. Irradiation at 313 nm results in a photoracemization quantum yield of 0.05 +/- 0.01 and 0.008 +/- 0.002 mol/einstein, respectively. The results of this work and previous studies on the photochemistry of cis- and trans-Rh(en)/sub 2/(OH)X/sup n+/ (X = OH, H/sub 2/O) and cis- and trans-Rh(en)/sub 2/(H/sub 2/O)/sub 2//sup 3 +/ are consistent with a photochemistry mechanism involving excitation, ligand labilization, rearrangement of an excited-state, five-coordinate fragment, relaxation, and solvent addition. Ratios of the photochemical quantum yields for cis-L to cis-rac and cis to trans conversions agree with the conclusion that Rh(en)/sub 2/(OH)/sup 2 +/* is the species undergoing rearrangement in both the dihydroxo and aquo hydroxo systems. 24 references, 2 tables.
- Research Organization:
- Clemson Univ., SC
- OSTI ID:
- 5973496
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:22
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
PHOTOCHEMISTRY
PHOTOLYSIS
STEREOCHEMISTRY
AQUEOUS SOLUTIONS
EXCITED STATES
EXPERIMENTAL DATA
LIGANDS
QUANTUM EFFICIENCY
RACEMATES
RACEMIZATION
RELAXATION
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DECOMPOSITION
DISPERSIONS
EFFICIENCY
ENERGY LEVELS
INFORMATION
MIXTURES
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry