Concurrent electrophilic and oxidative pathways for reactions of. cap alpha. -hydroxyalkyl and. cap alpha. -alkoxyalkyl complexes of chromium(III) with mercury(II) ions
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The reactions of Hg/sup 2 +/ with a number of ..cap alpha..-hydroxyalkyl and ..cap alpha..-alkoxyalkyl complexes of chromium(III) were studied. The lowest members of both series, CrCH/sub 2/OH/sup 2 +/ and CrCH/sub 2/OCH/sub 3//sup 2 +/, react with Hg/sup 2 +/ in an acid-independent electrophilic substitution reaction with the reaction constant rho = 10. The organomercurials formed are unstable and decompose rapidly to yield Hg/sup 0/. All the other organochromium complexes studied react with Hg/sup 2 +/ in acid-dependent electron-transfer reactions. (..cap alpha..-Hydroxyisopropyl(chromium ion, CrC(CH/sub 3/)/sub 2/OH/sup 2 +/, undergoes a one-electron transfer reaction, producing Cr/sup 2 +/ and Hg/sup +/ with k (M/sup -1/ s/sup 1/) = 166 + 467/(H/sup +/), while (..cap alpha..-ethoxyethyl)chromium ion, CrCH(CH/sub 3/)OC/sub 2/H/sub 5//sup 2 +/, reacts in a two-electron redox process, yielding Cr/sup 3 +/ and Hg/sup 0/, k (M/sup -1/s/sup -1/) = 0.535/(H/sup +/). (..cap alpha..-Hydroxyethyl)chromium ion, CrCH(CH)/sub 3/OH/sup 2 +/ reacts by both routes, k(M/sup -1/ s/sup -1/) = 4.11/(H/sup +/), with approx. 15% participation from the one-electron path and approx. 85% from the two-electron path. The effect of Cr/sup 2 +/ and Co(NH/sub 3/)/sub 5/F/sup 2 +/ (a specific scavenger for Cr/sup 2 +/) on the kinetics and stoichiometry of the reactions is discussed.
- Research Organization:
- Ames Lab., IA
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6040848
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:10; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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· J. Am. Chem. Soc.; (United States)
·
OSTI ID:5611455
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Thesis/Dissertation
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Tue Dec 31 23:00:00 EST 1985
·
OSTI ID:6855645
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
COMPLEXES
DATA
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
KINETICS
MERCURY COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
REACTION KINETICS
REDUCTION
TRANSITION ELEMENT COMPLEXES
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
COMPLEXES
DATA
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
KINETICS
MERCURY COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
REACTION KINETICS
REDUCTION
TRANSITION ELEMENT COMPLEXES