Reactions of the 17-electron bis(dimethylglyoximato)(triphenylphosphine)rhodium(II) radical with cobalt(III) complexes
- 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), Journal Name: Inorganic Chemistry; (USA) Vol. 28:3; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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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
Thermal and photochemical studies of a monomeric rhodium(II) radical
Related Subjects
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AMINES
AMMONIUM COMPLEXES
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
DATA
DECOMPOSITION
DIMETHYLGLYOXIME
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
LASER RADIATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIMES
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
REAGENTS
REDOX REACTIONS
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES