Matrix photochemistry of ethyltrioxorhenium(VII), C₂H₅ReO₃: Tautomerisation via ¦Â-hydrogen migration with the sequential formation of two different ethene derivatives

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• 作者：Leigh J. Morris ; Tim M. Greene ; Jennifer C. Green ; Anthony J. Downs
• 关键词：Matrix isolation ; Tautomerisation ; Ethyltrioxorhenium(VII) ; Ethene complexes ; Photochemistry
• 刊名：Journal of Molecular Structure
• 出版年：2012
• 出版时间：10 October, 2012
• 年：2012
• 卷：1025
• 期：Complete
• 页码：84-91
• 全文大小：582 K

文摘

IR spectroscopic measurements have been used to chart the matrix photochemistry of ethyltrioxorhenium(VII). Broad-band UV-visible light (200 ¡Ü ¦Ë ¡Ü 800 nm) results in the migration of a ¦Â-hydrogen atom of the ethyl group with the sequential formation of two tautomers, the first a weakly OH-bound ethene complex, C₂H₄¡¤HOReO₂, and the second the ¦Ç²-coordinated ethene derivative (¦Ç²-C₂H₄)Re(OH)O₂. There is no evidence of the carbene derivative CH₃CHRe(OH)O₂ which might have been expected by analogy with the behaviour of methyltrioxorhenium, CH₃ReO₃, under similar circumstances. Assignments of the IR absorption bands are made and their carriers identified on the basis of experiments with C₂D₅ReO₃ and CH₃CD₂ReO₃ and by comparison with the vibrational properties either forecast by density functional theory (DFT) calculations or determined experimentally for related molecules.