Laser Chemistry

Laser Chemistry / 1999 / Article
Special Issue

Proceedings of the Eighth Conference on Time-Resolved Vibrational Spectroscopy

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Open Access

Volume 19 |Article ID 79161 | 10 pages | https://doi.org/10.1155/1999/79161

Femtosecond Infrared Studies of Chemical Bond Activation

Received22 Oct 1997

Abstract

The identification of the intermediates observed in bond activation reactions involving organometallic complexes on time scales from femtoseconds to milliseconds has been accomplished through the use of ultrafast infrared spectroscopy. C—H bond activation by the molecule Tp*Rh(CO)2 showed a final activation time of 200 ns in cyclic solvents, indicating a reaction barrier of 8.3 kcal/mol. An important intermediate is the partially dechelated η2-Tp*Rh(CO)(S) solvent complex, which was formed 200 ps after the initial photoexcitation. Si—H bond activation by CpM(CO)3 (M=Mn, Re) showed some product formation in less than 5 ps, indicating that the Si—H activation reaction is barrierless. The activated product was formed on several timescales, from picoseconds to nanoseconds, suggesting that there are different pathways for forming final product which are partitioned by the initial photoexcitation.

Copyright © 1999 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


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