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 · Wed Oct 25 00:00:00 EDT 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00204a008· OSTI ID:7069928

Belt, S T; McCamley, A; Perutz, R N ^[1]; Grevels, F W; Klotzbuecher, W E ^[2]

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1. Univ. of York (England)
2. 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), Vol. 111:22; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
PHOTOCHEMISTRY
PHOTOLYSIS
BONDING
CALCULATION METHODS
CHEMICAL ACTIVATION
DATA ANALYSIS
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
REACTION INTERMEDIATES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DECOMPOSITION
FABRICATION
INFORMATION
JOINING
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
TRANSITION ELEMENT COMPLEXES
400200* - Inorganic
Organic
& Physical Chemistry
400500 - Photochemistry