Photochemical oxidative addition reactions of (eta/sup 5/-cyclopentadienyl)bis(ethene)rhodium with dihydrogen and trialkylsilanes: formation and isolation of rhodium(III) and rhodium(V) hydrides
Journal Article
·
· Organometallics; (United States)
Photolysis of CpRh(C/sub 2/H/sub 4/)/sub 2/ (1; Cp = eta/sup 5/-C/sub 5/H/sub 5/) in benzene or toluene in the presence of R/sub 3/SiH (R = Me, Et) yields CpRh/sup III/(C/sub 2/H/sub 4/)(SiEt/sub 3/)H (2), CpRh/sup V/(SiEt/sub 3/)/sub 2/(H)/sub 2/ (3), ethane, and triethylsilane. By appropriate choice of conditions the reaction can be controlled to enable the isolation of either 2 or 3. The identification of 2 and 3 are secured by multinuclear NMR. Photolysis of 1 in liquid xenon at 170 K under a 10-bar pressure of hydrogen yields CpRh(C/sub 2/H/sub 4/)(H)/sub 2/ (4). Complex 4 and several /sup 2/H-substituted analogues are identified by FTIR spectroscopy. 4 may be converted to CpRh(C/sub 2/H/sub 4/)(D)/sub 2/ by photolysis under D/sub 2/. Ethane is generated in a slow thermal process subsequent to photolysis that may be followed by FTIR or NMR spectroscopy in liquid xenon. The dihydride 4 has not been detected by NMR when 1 is photolyzed in toluene solution or LXe under lower hydrogen pressures, even though ethane is generated.
- Research Organization:
- Univ. of York, (England)
- OSTI ID:
- 7190543
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:7; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKENES
CHEMICAL REACTIONS
CHEMISTRY
CYCLOALKENES
DATA
ELEMENTS
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
OXIDATION
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
REFRACTORY METAL COMPOUNDS
RESONANCE
RHODIUM COMPOUNDS
SILANES
SILICON COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400500* -- Photochemistry
ALKENES
CHEMICAL REACTIONS
CHEMISTRY
CYCLOALKENES
DATA
ELEMENTS
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
OXIDATION
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
REFRACTORY METAL COMPOUNDS
RESONANCE
RHODIUM COMPOUNDS
SILANES
SILICON COMPOUNDS
TRANSITION ELEMENT COMPOUNDS