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Decomposition of chemically activated ethyltrimethylgermane the arrhenius A ‐factors for rupture of group IVA—methyl bonds
Author(s) -
Scott R. L.,
Richardson A. E.,
Simons J. W.,
Hase W. L.
Publication year - 1975
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550070406
Subject(s) - chemistry , diazomethane , arrhenius equation , decomposition , extrapolation , germanium , methyl group , photodissociation , reaction rate constant , methyl radical , activation energy , medicinal chemistry , silicon , computational chemistry , photochemistry , alkyl , radical , organic chemistry , kinetics , physics , mathematical analysis , mathematics , quantum mechanics
The decomposition rate of chemically activated ethyltrimethylgermane from the reaction 1 CH 2 + (CH 3 ) 4 Ge, where 1 CH 2 was produced from diazomethane photolysis at 3660 Å, is 8.6 × 10 5 sec −1 . This result combined with RRKM theory and critical energy estimates yields an Arrhenius A factor of log[ A (sec −1 )/methyl] = 14.7 ± 0.8 for methyl rupture from germanium. Log A values for methyl rupture from carbon, silicon, and germanium linearly correlate with the vibrational‐rotational entropies of the corresponding tetramethyls. Extrapolation predicts log[ A (sec −1 )/methyl] = 14.4 and 14.3 for methyl rupture from tin and lead, respectively.