Decomposition of chemically activated ethyltrimethylgermane the arrhenius A‐factors for rupture of group IVA—methyl bonds

R. L. Scott; A. E. Richardson; J. W. Simons; W. L. Hase

doi:10.1002/kin.550070406

Decomposition of chemically activated ethyltrimethylgermane the arrhenius A‐factors for rupture of group IVA—methyl bonds

R. L. Scott, A. E. Richardson, J. W. Simons, W. L. Hase

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

The decomposition rate of chemically activated ethyltrimethylgermane from the reaction ¹CH₂ + (CH₃)₄Ge, where ¹CH₂ was produced from diazomethane photolysis at 3660 Å, is 8.6 × 10⁵ 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.

Original language	English
Pages (from-to)	547-555
Number of pages	9
Journal	International Journal of Chemical Kinetics
Volume	7
Issue number	4
DOIs	https://doi.org/10.1002/kin.550070406
State	Published - Jul 1975

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@article{b782d4f45be04db3a15085412844f2df,

title = "Decomposition of chemically activated ethyltrimethylgermane the arrhenius A‐factors for rupture of group IVA—methyl bonds",

abstract = "The decomposition rate of chemically activated ethyltrimethylgermane from the reaction 1CH2 + (CH3)4Ge, where 1CH2 was produced from diazomethane photolysis at 3660 {\AA}, is 8.6 × 105 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.",

author = "Scott, {R. L.} and Richardson, {A. E.} and Simons, {J. W.} and Hase, {W. L.}",

year = "1975",

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journal = "International Journal of Chemical Kinetics",

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T1 - Decomposition of chemically activated ethyltrimethylgermane the arrhenius A‐factors for rupture of group IVA—methyl bonds

AU - Scott, R. L.

AU - Richardson, A. E.

AU - Simons, J. W.

AU - Hase, W. L.

PY - 1975/7

Y1 - 1975/7

N2 - The decomposition rate of chemically activated ethyltrimethylgermane from the reaction 1CH2 + (CH3)4Ge, where 1CH2 was produced from diazomethane photolysis at 3660 Å, is 8.6 × 105 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.

AB - The decomposition rate of chemically activated ethyltrimethylgermane from the reaction 1CH2 + (CH3)4Ge, where 1CH2 was produced from diazomethane photolysis at 3660 Å, is 8.6 × 105 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.

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