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Communication: The insertion of silylene in CH bonds; rate constant limits and the energy barrier

✍ Scribed by Rosa Becerra; Robin Walsh


Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
113 KB
Volume
31
Category
Article
ISSN
0538-8066

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✦ Synopsis


The technique of laser flash photolysis has been used to set limits on the rate constants for the bimolecular reactions of SiH 2 with methane (CH 4 ) and tetramethylsilane (SiMe 4 ) at both ambient and elevated temperatures (ca 600 K). These limits show that the energy barriers to insertion reactions of SiH 2 in the C9 H bonds of CH 4 are at least 45(Ϯ6) kJ and in the C9 H and/or Si 9 C bonds of SiMe 4 are at least 23(Ϯ6) kJ The best Ϫ1 Ϫ1 mol mol . thermochemical estimate of the activation energy for is 59(Ϯ12) kJ Reasons Ϫ1 SiH ϩ CH mol . 2 4 for the greatly diminished reactivity of SiH 2 with C9H as compared with Si 9 H bonds are discussed.