Reactions of the 17-electron bis(dimethylglyoximato)(triphenylphosphine)rhodium(II) radical with cobalt(III) complexes
Journal Article
·
· Inorganic Chemistry; (USA)
- Ames Lab., IA (USA)
The rhodium(II) radical Rh(dmgH){sub 2}PPh{sub 3}, formed by the laser flash photolysis of the dimer, is oxidized by a range of cobalt(III) complexes of the type XCo(dmgH){sub 2}PPh{sub 3} and Co(NH{sub 3}){sub 5}X{sup 2+}, where X is a halogen or pseudohalogen. The second-order rate constants measured at 23{degree}C in 95% ethanol for these reactions fall within the range 2.9 {times} 10{sup 6}-3.0 {times} 10{sup 8} L mol{sup {minus}1} s{sup {minus}1}. For the halides, the normal reactivity order is observed, i.e., Br{sup {minus}} > Cl{sup {minus}} > F{sup {minus}}. The mechanisms of these reactions are discussed, it is concluded that they all occur by inner-sphere pathways. 16 refs., 2 figs., 2 tabs.
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5144295
- Journal Information:
- Inorganic Chemistry; (USA), Vol. 28:3; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Reactions of the 17-electron bis(dimethylglyoximato)(triphenylphosphine)rhodium(II) radical
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Wed Sep 07 00:00:00 EDT 1988
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Photochemical generation of [Rh(dmgH)[sub 2]PPh[sub 3]][sub 2] from [CpW(CO)[sub 3]][sub 2] and XRh(dmgH)[sub 2]PPh[sub 3] (X = Cl, Br) with intermediate 17-electron tungsten and rhodium radicals
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Thu Apr 01 00:00:00 EST 1993
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Thermal and photochemical studies of a monomeric rhodium(II) radical
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OSTI ID:5144295
Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM COMPLEXES
REDOX REACTIONS
COBALT COMPLEXES
DIMETHYLGLYOXIME
HALIDES
PHOSPHINES
RHODIUM COMPLEXES
EXPERIMENTAL DATA
LASER RADIATION
PHOTOLYSIS
AMINES
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIMES
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATIONS
REAGENTS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM COMPLEXES
REDOX REACTIONS
COBALT COMPLEXES
DIMETHYLGLYOXIME
HALIDES
PHOSPHINES
RHODIUM COMPLEXES
EXPERIMENTAL DATA
LASER RADIATION
PHOTOLYSIS
AMINES
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIMES
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATIONS
REAGENTS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry