Reactions of the 17-electron bis(dimethylglyoximato)(triphenylphosphine)rhodium(II) radical
Journal Article
·
· Inorg. Chem.; (United States)
The indicated metal-centered radical arises from the laser-flash photolysis of the dinuclear complex (Rh(dmgH)/sub 2/PPh/sub 3/)/sub 2/. In the absence of other reagents the radical (which shows an absorption maximum at 580 nm, /epsilon/ = 2 /times/ 10/sup 3/L mol/sup /minus/1/ cm/sup /minus/1/) dimerizes rapidly, with k/sub D/ = 2.3 /times/ 10/sup 8/L mol/sup /minus/1/ s/sup /minus/1/ in 95% ethanol. The metal-centered radical reacts rapidly with O/sub 2/, k = 1.4 /times/ 10/sup 9/ L mol/sup /minus/1/ s/sup /minus/1/, with the first step assigned to the formation of a 1:1 oxygen adduct. This reaction ultimately yields hydrogen peroxide. The reactions between Rh(dmgH)/sub 2/PPh/sub 3/ and a wide range of alkyl halides have also been studied. The rate constants k/sub RX/ span a wide range, from /approx/ 4 /times/ 10/sup 2/ (CHCl/sub 3/) to 9 /times/ 10/sup 8/ (CBr/sub 4/). There is an approximate correlation between log k/sub RX/ and the carbon-halogen bond dissociation energy. A correlation is also found with the half-wave potential for the reaction RX + e/sup /minus// /yields/ R/sup /center dot// + X/sup /minus//. The mechanism of the reactions with alkyl halides is discussed, and it seems probably that these reactions proceed by halogen atom abstraction. 24 references, 5 figures, 2 tables.
- Research Organization:
- Iowa State Univ., Ames (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5852635
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:18; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AMINES
AROMATICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
LASER RADIATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIMES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AMINES
AROMATICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
LASER RADIATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIMES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES