Mechanistic chemistry of some transition-metal complexes
The reactivity of several pentaaquo-..cap alpha..-hydroxyalkylchromium(III) complexes including (H/sub 2/O)/sub 5/CrCH(C/sub 2/H/sub 5/)OH/sup 2 +/, CrC(C/sub 3/)(C/sub 2/H/sub 5/)OH/sup 2 +/, CrC(C/sub 2/H/sub 5/)/sub 2/OH/sup 2 +/, CrC(CH/sub 3/)(i-C/sub 3/H/sub 7/)OH/sup 2 +/ and CrC(C/sub 3/) (t-C/sub 4/H/sub 9/)OH/sup 2 +/ was examined. The chromium-carbon bond was found to cleave by both heterolytic and homolytic pathways. One ..cap alpha..-alkylchromium(III) complex, CrC(CH/sub 3/)/sub 2/OCH(CH/sub 3/)/sub 2//sup 2 +/, was also studied; its homolysis rate constant was determined. It was also found to undergo rearrangement in dilute perchloric acid to CrC(CH/sub 3/)/sub 2/OH/sup 2 +/. The reactions of five alkylchromium(III) complexes with Cu/sup 2 +/ or Fe/sup 3 +/ were investigated. The predominant pathway for reactions with both oxidants was found to be inversely dependent on the acid concentration in the range studied. Three dicobalt(II) complexes of Schiff base macrocyclic ligands with N/sub 2/O/sub 2/ chelating sites were prepared. These complexes were all based upon the tetra(salicylideneamino)benzene unit. The complexes were characterized by their electronic spectra and elemental analysis. The dicobalt(II) complexes are easily oxidized to the dicobalt(III) analogs. The dicobalt(III) complexes may be re-reduced to the parent dicobalt(II) complexes with CrCl/sub 2/. One organometallic derivative, (CH/sub 3/Co)/sub 2/(5-Bu/sup t/sal/sub 4/)bz, was prepared. It was characterized by its reaction with Hg(II) and its photodecomposition to the dicobalt(II) complex under anaerobic conditions and to dicobalt(III) under aerobic conditions.
- Research Organization:
- Ames Lab., IA (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5845980
- Report Number(s):
- IS-T-954; ON: DE82005577
- Resource Relation:
- Other Information: Thesis
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHROMIUM COMPLEXES
CHEMICAL REACTIONS
COBALT COMPLEXES
COPPER COMPOUNDS
IRON COMPOUNDS
CHEMICAL REACTION KINETICS
DECOMPOSITION
OXIDATION
REDUCTION
SCHIFF BASES
SPECTRA
COMPLEXES
IMINES
KINETICS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties