Photochemical generation and chemical reactivity of hydridopentaaquochromium(III) ions
Journal Article
·
· Inorg. Chem.; (United States)
The complex (H/sub 2/O)/sub 5/CrH/sup 2 +/ was prepared by UV flash photolysis of aqueous chromium(II) perchlorate solutions in dilute perchloric acid. This species /sup 1//sub max/ = 385 +- 5 nm) has a short lifetime owing to its rapid reaction with H/sub 3/O/sup +/ (k = 1.0 +- 0.1) x 10/sup 4/ M/sup -1/ s/sup -1/ at 26/sup 0/C and ..mu.. = 0.20 M) to evolve hydrogen. The rate constant was studied as a function of ionic strength, confirming the 2+ charge, and a ..mu.. = 0.20 M as a function of temperature, providing the activation parameters ..delta..H double dagger = 26.4 +- 0.9 kJ mol/sup -1/, ..delta..S double dagger = -79.9 +- 2.9 J mol/sup -1/ K/sup -1/. The acidolysis of CrH/sup 2 +/ occurs 2 x 10/sup 6/ times more rapidly than that of methylpentaaquochromium(III) ion, (H/sub 2/O)/sub 5/CrCH/sub 3//sup 2 +/. Protonolysis of CrH/sup 2 +/ in H/sub 3/O/sup +/ as compared to CrD/sup 2 +/ in D/sub 3/O/sup +/ shows an appreciable kinetic isotope effect (k/sub H//k/sub D/ = 4.8) as does the protonolysis of CrCH/sub 3//sup 2 +/ in the same two solvents (k/sub H//k/sub D/ = 6.3). The mechanism in both cases involves O . H bond breaking more so than chromium-hydrogen (or chromium-carbon) cleavage.
- Research Organization:
- Iowa State Univ., Ames
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5646089
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 20:12; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500 -- Photochemistry
ABSORPTION SPECTRA
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHLORINE COMPOUNDS
CHROMIUM COMPLEXES
CHROMIUM COMPOUNDS
CHROMIUM HYDRIDES
COMPLEXES
DATA
DEUTERIUM
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
OXYGEN COMPOUNDS
PERCHLORATES
REACTION INTERMEDIATES
REACTION KINETICS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TEMPERATURE EFFECTS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500 -- Photochemistry
ABSORPTION SPECTRA
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHLORINE COMPOUNDS
CHROMIUM COMPLEXES
CHROMIUM COMPOUNDS
CHROMIUM HYDRIDES
COMPLEXES
DATA
DEUTERIUM
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
OXYGEN COMPOUNDS
PERCHLORATES
REACTION INTERMEDIATES
REACTION KINETICS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TEMPERATURE EFFECTS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS