Intermediates in the time-resolved and matrix photochemistry of (. eta. sup 5 -cyclopentadienyl)rhodium complexes: Roles of alkane activation and rhodium-rhodium bond formation
Journal Article
·
· Journal of the American Chemical Society; (USA)
- Univ. of York (England)
- Max-Planck Institut fuer Strahlenchemie (Germany, F.R.)
Pulsed laser photolysis studies of solutions of Cp{sub 2}Rh{sub 2}(CO){sub 3}, CpRh(CO){sub 2}, and CpRh(C{sub 2}H{sub 4})CO (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}) are reported using UV/vis and IR detection. Isotopic labeling and polarized photolysis demonstrates that the Rh{sub 2}(CO){sub 2} unit is planar with CO bridges perpendicular to the RhRh axis. Metal-metal bond fission of Cp{sub 2}Rh{sub 2}(CO){sub 3} is observed only in CO-doped matrices. The major photoproduct of Cp{sub 2}Rh{sub 2}(CO){sub 3} in solution is (CpRh({mu}-CO)){sub 2}, which reacts with CO to re-form starting material. The first observable product of photolysis of CpRh(CO){sub 2} in cyclohexane at room temperature is CpRh(CO)(C{sub 6}H{sub 11})H, formed by insertion of CpRhCO into the solvent C-H bonds within 400 ns. The IR experiments show that photolysis of CpRh(C{sub 2}H{sub 4})CO gives a higher yield of CpRh(CO)(C{sub 6}H{sub 11})H than that from CpRh(CO){sub 2}.
- OSTI ID:
- 7069928
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:22; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Sub-picosecond IR study of the reactive intermediate in an alkane C-H bond activation reaction by CpRh(CO){sub 2}
Journal Article
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Tue Mar 15 23:00:00 EST 1988
· J. Am. Chem. Soc.; (United States)
·
OSTI ID:7004401
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
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Fri Jul 01 00:00:00 EDT 1988
· Organometallics; (United States)
·
OSTI ID:7190543
Sub-picosecond IR study of the reactive intermediate in an alkane C-H bond activation reaction by CpRh(CO){sub 2}
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Mon Aug 03 00:00:00 EDT 1998
· Organometallics
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OSTI ID:655372
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200* -- Inorganic
Organic
& Physical Chemistry
400500 -- Photochemistry
BONDING
CALCULATION METHODS
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DATA ANALYSIS
DECOMPOSITION
EXPERIMENTAL DATA
FABRICATION
INFORMATION
JOINING
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
REACTION INTERMEDIATES
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
400200* -- Inorganic
Organic
& Physical Chemistry
400500 -- Photochemistry
BONDING
CALCULATION METHODS
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DATA ANALYSIS
DECOMPOSITION
EXPERIMENTAL DATA
FABRICATION
INFORMATION
JOINING
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
REACTION INTERMEDIATES
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES