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Issue 18, 2009
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Time-resolved gas-phase kinetic study of the germylene addition reaction, GeH2 + CH3C[triple bond, length as m-dash]CCH3

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Abstract

Time-resolved kinetic studies of the reaction of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with 2-butyne, CH3C[triple bond, length as m-dash]CCH3. The reaction was studied in the gas phase over the pressure range 1–100 Torr in SF6 bath gas, at five temperatures in the range 300–556 K. The second order rate constants obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equation:log(k/cm3 molecule−1 s−1) = (−10.46 ± 0.06) + (5.16 ± 0.47) kJ mol−1/ RT ln 10Calculations of the energy surface of the GeC4H8 reaction system were carried out employing the additivity principle, by combining previous quantum chemical calculations of related reaction systems. These support formation of 1,2-dimethylvinylgermylene (rather than 2,3-dimethylgermirene) as the end product. RRKM calculations of the pressure dependence of the reaction are in reasonable agreement with this finding. The reactions of GeH2 with C2H2 and with CH3C[triple bond, length as m-dash]CCH3 are compared and contrasted.

Graphical abstract: Time-resolved gas-phase kinetic study of the germylene addition reaction, GeH2 + CH3C [[triple bond, length as m-dash]] CCH3

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Supplementary files

Article information


Submitted
28 Nov 2008
Accepted
05 Feb 2009
First published
05 Mar 2009

Phys. Chem. Chem. Phys., 2009,11, 3539-3546
Article type
Paper

Time-resolved gas-phase kinetic study of the germylene addition reaction, GeH2 + CH3C[triple bond, length as m-dash]CCH3

R. Becerra and R. Walsh, Phys. Chem. Chem. Phys., 2009, 11, 3539
DOI: 10.1039/B821330E

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