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Communication: The insertion of silylene in CH bonds; rate constant limits and the energy barrier
Author(s) -
Becerra Rosa,
Walsh Robin
Publication year - 1999
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/(sici)1097-4601(1999)31:5<393::aid-kin9>3.0.co;2-2
Subject(s) - chemistry , tetramethylsilane , silylene , flash photolysis , reaction rate constant , activation energy , reactivity (psychology) , methane , bond energy , photochemistry , molecule , kinetics , organic chemistry , silicon , medicine , physics , alternative medicine , pathology , quantum mechanics
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 CH bonds of CH 4 are at least 45(±6) kJ mol −1 and in the CH and/or SiC bonds of SiMe 4 are at least 23(±6) kJ mol −1 . The best thermochemical estimate of the activation energy for SiH 2 +CH 4 is 59(±12) kJ mol −1 . Reasons for the greatly diminished reactivity of SiH 2 with CH as compared with SiH bonds are discussed. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 393–395, 1999