Kinetic studies of organochromium(III) cations and their hydrido analog

Thesis/Dissertation · Thu Jan 01 04:00:00 EST 1981

OSTI ID:5481453

Ryan, D A.P.

The complex HOCH/sub 2/CH/sub 2/Cr(H/sub 2/)/sub 5//sup 2 +/ and HCr(H/sub 2/O)/sub 5//sup 2 +/ were prepared by flash photolysis in dilute aqueous HClO/sub 4/ and by uv flash photolysis in aqueous Cr(III) perchlorate solutions, respectively. The kinetics of the reaction of both complex species with H/sub 3/O/sup +/ were studies and rate laws for the reactions were determined. The deuterated complex DCr(D/sub 2/O)/sub 5//sup 2 +/ showed a large kinetic isotope effect in its reaction with D/sub 3/O/sup +/ which is similar in magnitude to the acidolysis of the CH/sub 3/Cr(D/sub 2/O)/sub 5//sup 2 +/ ion by D/sub 3/O/sup +/. These findings are supportive of a mechanism where the O-H bond breaking is the rate-limiting reaction for both complexes. Protonolysis of HCr(H/sub 2/O)/sub 5//sup 2 +/ was proposed to occur via a nonlinear three-center transition state in which the H-Cr bond is still intact. (BLM)

• OSTI ID: 5481453
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500* -- Photochemistry
AQUEOUS SOLUTIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
CHROMIUM COMPLEXES
CHROMIUM COMPOUNDS
CHROMIUM PERCHLORATES
COMPLEXES
DECOMPOSITION
DEUTERIUM
DISPERSIONS
HALOGEN COMPOUNDS
HYDROGEN ISOTOPES
IONS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MIXTURES
MOLECULAR IONS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXONIUM IONS
OXYGEN COMPOUNDS
PERCHLORATES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
SOLUTIONS
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS