A novel photochemical, pH-controlled synthesis of organochromium complexes
Journal Article
·
· Inorganic Chemistry; (United States)
- Ames Lab., IA (United States)
The irradiation of aqueous solutions of Cr{sup 2+} and RX (R = primary, secondary, and tertiary alkyl; X = Br, Cl) at 254 nm and pH 3 yields the organochromium cations (H{sub 2}O){sub 5}CrR{sup 2+}. The method is based on the photochemical generation of hydrated electrons and subsequent reduction of the alkyl halides to carbon-centered radicals. The colligation with Cr{sup 2+} then yields the desired organochromium complexes. In the presence of alcohols as cosolvents, the nature of the group R in (H{sub 2}O){sub 5}CrR{sup 2+} depends on the pH. At pH 3, R is derived from RX, and at pH 0, from the alcohol. The photochemical method was used to prepare, among others, the novel tert-butylchromium(III) ion (H{sub 2}O){sub 5}CrC(CH{sub 3}){sub 3}{sup 2+}. In the presence of scavengers for Cr{sup 2+} and/or {sm bullet}C(CH{sub 3}){sub 3} this complex decomposes rapidly by homolysis of the Cr-C bond, k{sub h} = 0.60 s{sup {minus}1} at 25C.
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 7011801
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:6; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALCOHOLS
AMBIENT TEMPERATURE
AQUEOUS SOLUTIONS
BROMINE COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
CHROMATOGRAPHY
CHROMIUM COMPLEXES
COMPLEXES
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
GAS CHROMATOGRAPHY
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
HYDROXYL RADICALS
KINETICS
LIGANDS
MIXTURES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PH VALUE
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADIATIONS
RADICALS
REACTION KINETICS
SEPARATION PROCESSES
SOLUTIONS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION
400500* -- Photochemistry
ALCOHOLS
AMBIENT TEMPERATURE
AQUEOUS SOLUTIONS
BROMINE COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
CHROMATOGRAPHY
CHROMIUM COMPLEXES
COMPLEXES
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
GAS CHROMATOGRAPHY
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
HYDROXYL RADICALS
KINETICS
LIGANDS
MIXTURES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PH VALUE
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADIATIONS
RADICALS
REACTION KINETICS
SEPARATION PROCESSES
SOLUTIONS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION