Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00028a019· OSTI ID:6215120
; ;  [1]
  1. Iowa State Univ., Ames (United States)
+ Show Author Affiliations
Laser flash photolysis of [CpW(CO)[sub 3]][sub 2] in a CH[sub 3]CN solution containing XRh(dmgH)[sub 2]PPh[sub 3] (X is Cl, Br) leads to CpW(CO)[sub 3]X and [Rh(dmgH)[sub 2]PPh[sub 3]][sub 2]. The reaction proceeds by way of two different 17-electron organometallic radical intermediates. The W-W bond of [CpW(CO)[sub 3]][sub 2] cleaves in the laser flash to give CpW(CO)[sub 3] radicals. The tungsten radicals abstract a halogen atom from the halorhodium complex, k[sub Cl] = (9.2 [+-] 0.4) [times] 10[sup 7] and k[sub Br] = (1.57 [+-] 0.05) [times] 10[sup 8] L mol[sup [minus]1] s[sup [minus]1], forming the 17-electron radical Rh(dmgH)[sub 2]PPh[sub 3] that is observed spectroscopically at 580 nm. The Rh(dmgH)[sub 2]PPh[sub 3] radicals subsequently dimerize, k = 2.1 [times] 10[sup 8] L mol[sup [minus]1] s[sup [minus]1], to yield [Rh(dmgH)[sub 2]PPh[sub 3]][sub 2], observed spectroscopically at 452 nm. 34 refs., 1 fig.
DOE Contract Number:
W-7405-ENG-82
OSTI ID:
6215120
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:4; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English

Similar Records

Electron-transfer reactions of 17-electron and 19-electron organometallic radicals, CpW(CO)[sub 3] and CpW(CO)[sub 3]PPh[sub 3]
Journal Article · Fri Oct 01 00:00:00 EDT 1993 · Organometallics; (United States) · OSTI ID:5576229
Reactions of the 17-electron bis(dimethylglyoximato)(triphenylphosphine)rhodium(II) radical with cobalt(III) complexes
Journal Article · Tue Feb 07 23:00:00 EST 1989 · Inorganic Chemistry; (USA) · OSTI ID:5144295
Thermal and photochemical studies of a monomeric rhodium(II) radical
Journal Article · Wed Dec 31 23:00:00 EST 1980 · J. Am. Chem. Soc.; (United States) · OSTI ID:5807810

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
CHEMICAL REACTIONS
COMPLEXES
DIMERIZATION
ELECTROMAGNETIC RADIATION
LASER RADIATION
MATHEMATICAL MODELS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYMERIZATION
RADIATIONS
RADICALS
RHODIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES