Flash infrared kinetics of the photochemistry of Tp*Rh(CO)2 and Bp*Rh(CO)2 in Liquid Xenon Solution

Organometallics

Volumn 19, Issue 17, 2000, Pages 3442-3446

  Yeston, Jake S ^a   McNamara, Bruce K ^a   Bergman, Robert G ^a   Moore, C Bradley ^a  

^a LAWRENCE BERKELEY NATIONAL LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; ADDITION REACTIONS; CARBON MONOXIDE; CHEMICAL BONDS; COMPLEXATION; INFRARED SPECTROSCOPY; PHOTOLYSIS; RATE CONSTANTS; SOLUTIONS; XENON;

FLASH INFRARED KINETIC SPECTROSCOPY; PYRIDINE;

RHODIUM COMPOUNDS;

EID: 0034245676     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om000238w     Document Type: Article

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30. 2 pulse reached the sample, corresponding to an effective energy per pulse of approximately 10 mJ.
31. -1. This is due to a steady depletion of substrate during data collection, coupled with power fluctuations and wavelength-dependent signal-to-noise ratios inherent to the probe laser. Consequently, a thorough investigation of the temperature dependence of relative band intensities was not pursued.
32. Due to the relatively low solubility of 1 in Xe, attempts to isolate these photoproducts were unsuccessful. We were also unable to observe bands for the products in FTIR spectra; we observed only the disappearance of the CO bands of 1. Although 1 is more soluble in aromatic and chlorinated solvents than in Xe, photolysis in these solvents results in oxidative addition of C-H or C-C1 bonds across the Rh center, precluding an independent synthesis of the decomposition products formed in Xe.
33. The parent CO band recovered only 60% of its initial intensity in these experiments, suggesting that some decomposition was still occurring. Addition of a larger excess of CO could have increased the recovery percentage, but the rates of the recovery and transient decays would have become too fast to measure using our detection system.
34. -1 could not be observed in this experiment because the diode power at that wavelength was relatively low, and consequently the change in the parent band absorption upon photolysis was not above the noise level.
35. -1, perhaps indicative of dimer formation. This product band is not observed in the presence of buffering CO.
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45. 14 Consequently, it is likely that in Xe/cyclohexane mixtures, the observed transient bands result from both solvates.