Re-examination of 7,7′-dimethyl-7-germanorbornadiene photocleavage in solution and in organic glasses

Re-examination of 7,7′-dimethyl-7-germanorbornadiene photocleavage in solution and in organic... Dimethylgermylene and its Ge=Ge doubly bonded dimer, tetramethyldigermene, have been characterized directly in solution by 308-nm laser flash photolysis in n-hexane solution, as well as 254-nm photolysis in hydrocarbon glasses at t = 77 K. An absorption band maximum of λ max ≈ 430 nm and molar absorption coefficient of ε ≈ 2,700 M−1 cm−1 have been shown to be attributable to low-temperature glasses, while the absorption band maximum of λ max ≈ 480 nm and molar absorption coefficient of ε ≈ 2,400 M−1 cm−1 have been shown to be related to dimethylgermylene in n-hexane solution. The molar absorption coefficient of tetramethyldigermene (λ max ≈ 380 nm) was determined to be ε ≈ 84,000 M−1 cm−1. The germylene is formed via (formal) cheletropic photocycloreversion of 7,7′-dimethylgerma-1,4,5,6-tetraphenyl-2,3-benzo-norbornadiene. Tetramethyldigermene and 1,2,3,4-tetraphenylnaphthalene in the triplet state were formed, together with dimethylgermylene. We attempted to explain the various contradictory interpretations of experimental data existing in the literature on this reaction. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Re-examination of 7,7′-dimethyl-7-germanorbornadiene photocleavage in solution and in organic glasses

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Publisher
Springer Journals
Copyright
Copyright © 2010 by Springer Science+Business Media B.V.
Subject
Chemistry; Inorganic Chemistry ; Physical Chemistry ; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-010-0136-3
Publisher site
See Article on Publisher Site

Abstract

Dimethylgermylene and its Ge=Ge doubly bonded dimer, tetramethyldigermene, have been characterized directly in solution by 308-nm laser flash photolysis in n-hexane solution, as well as 254-nm photolysis in hydrocarbon glasses at t = 77 K. An absorption band maximum of λ max ≈ 430 nm and molar absorption coefficient of ε ≈ 2,700 M−1 cm−1 have been shown to be attributable to low-temperature glasses, while the absorption band maximum of λ max ≈ 480 nm and molar absorption coefficient of ε ≈ 2,400 M−1 cm−1 have been shown to be related to dimethylgermylene in n-hexane solution. The molar absorption coefficient of tetramethyldigermene (λ max ≈ 380 nm) was determined to be ε ≈ 84,000 M−1 cm−1. The germylene is formed via (formal) cheletropic photocycloreversion of 7,7′-dimethylgerma-1,4,5,6-tetraphenyl-2,3-benzo-norbornadiene. Tetramethyldigermene and 1,2,3,4-tetraphenylnaphthalene in the triplet state were formed, together with dimethylgermylene. We attempted to explain the various contradictory interpretations of experimental data existing in the literature on this reaction.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Mar 19, 2010

References

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