Complex ion chemistry. Progress report No. 3, July 1, 1970-June 30, 1971
The synthesis of 15 new Cr(III) complexes was completed during the report period: 1,2,3- and 1,2,6-Cr(trienH)/sub 3//sup 4 +/, Cr(trienH/sub 2/)(OH/sub 2/)/sub 4//sup 5 +/, Cr(trienH/sub 3/)(OH/sub 2/)/sub 5//sup 6 +/, 1,2,3- and 1,2,6-Cr(trienH)(OH/sub 2/)/sub 2/N/sub 2//sup 3 +/, Cr(trienH/sub 2/)(OH/sub 3/)/sub 3/N/sub 3//sup 4 +/, Cr(trienH/sub 3/)(OH2)/sub 4/N/sub 3//sup 5 +/, Cr(tetren)OH/sub 2//sup 3 +/, Cr(tetrenH)(OH/sub 2/)/sub 2//sup 4 +/, Cr(tetrenH/sub 2/)(OH/sub 2/)/sub 3//sup 5 +/, Cr(tetrenH/sub 3/)(OH/sub 2/)/sub 4//sup 6 +/, Cr(tetrenH/sub 4/)(OH/sub 2/)/sub 5//sup 7 +/. cis-Cr(dipy)/sub 2//sup -/(OH/sub 2/)Cl/sup 2 +/, and Cr(dipy)(OH/sub 2/)/sub 4//sup 3 +/. The complexes with protonated trien and tetren ligands represent interesting species with the amine ligand exhibiting less than its normal denticity. The d-d absorption spectra of all new complexes are reported. Kinetic studies of substitution reactions completed during the report period include 12 Cr(III) nitrito complexes, 4 Cr(III) aquotrien complexes, 5 Cr(III) aquotetren complexes, 2 Cr(III) 2,2'-dipyridyl complexes, 1 Co(III) aquodien complex, and 1 Co(III) tetren complex; work is still underway on 1,2,3- and 1,2,6-Cr(trienH)(OH/sub 2/)/sub 2/N/sub 3//sup 3 +/, Cr(trienH/sub 2/)/sub 3/N/sub 3//sup 4 +/, Cr(trienH/sub 3/)(OH/sub 2/)/sub 4/N/sub 3//sup 5 +/, and Co(NH/sub 3/)/sub 6//sup 3 +/. Kinetic studies of redox reactions finished during the report period are the spontaneous reduction of 1,2,3-Co(dien)(OH/sub 2/)/sub 3//sup 5 +/, and electron-transfer reactions involving Cr(II) as Cr(OH/sub 2/)/sub 6//sup 2 +/, and Cr(en)/sub 2//sup 2 +/ as reductant and either Co(NH/sub 3/)/sub 5/Cl/sup 2 +/ or various Cr(NH/sub 3/)/sub n/(OH/sub 2/)/sub 5-n/Cl/sup n+/ species as oxidant. The latter reactions bear on the interesting problem of the role of nonbridging ligands in the bridging mechanism of electron transfer. Spontaneous redox reactions still under investigation include Co(NH/sub 3/)/sub 5/OH/sub 2//sup 3 +/and its aquation products, and cis-Co(en)/sub 2/(OH/sub 2/)/sub 2//sup 3 +/. A new modification of the Staples method of azide analysis has been developed.
- Research Organization:
- University of Southern California, Los Angeles (USA). Dept. of Chemistry
- DOE Contract Number:
- AT03-76SF80034
- OSTI ID:
- 6324388
- Report Number(s):
- UCLA-34P170-20
- Country of Publication:
- United States
- Language:
- English
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ABSORPTION SPECTRA
AMINES
AZIDO COMPOUNDS
CHEMICAL ANALYSIS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
COMPLEXES
DIAZO COMPOUNDS
ELECTRON TRANSFER
KINETICS
LIGANDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
QUANTITATIVE CHEMICAL ANALYSIS
REACTION KINETICS
REDOX REACTIONS
RESEARCH PROGRAMS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES