Photochemistry of tricarbonyl (η5-cyclopentadienyl)(trifluoroacetyl)-molybdenum in a variety of frozen gas matrices at ca. 12 K: infrared spectroscopic evidence for carbon monoxide ejection and difluorocarbene formation by α-F elimination

Autor:	Andrew K. Campen, Khalil A. Mahmoud, Antony J. Rest, Paul A. Willis
Rok vydání:	1990
Předmět:	chemistry.chemical_compound Reaction mechanism chemistry Difluorocarbene Cyclopentadienyl complex Molybdenum Photodissociation Matrix isolation Infrared spectroscopy chemistry.chemical_element General Chemistry Photochemistry Carbon monoxide
Zdroj:	J. Chem. Soc., Dalton Trans.. :2817-2823
ISSN:	1364-5447 0300-9246
DOI:	10.1039/dt9900002817
Popis:	Infrared spectroscopic evidence including 13CO labelling is presented which shows that photolysis of [Mo(η5-C5H5)(CO)3(COCF3)] in frozen gas matrices (argon, methane, carbon monoxide, or nitrogen) at ca. 12 K affords stepwise ejection of CO to yield [Mo(η5-C5H5)(CO)3(CF3)]via the 16-electron species [Mo(η5-C5H5)(CO)2(COCF3)]. Subsequent photolysis of [Mo(η5-C5H5)-(CO)3(CF3)] produces further CO ejection reversibly to give the 16-electron species [Mo(η5- C5H5)-(CO)2(CF3)], which in nitrogen matrices undergoes a reversible reaction to produce cis-[Mo(η5- C5H5)-(CO)2(CF3)(N2)], while in other matrices a novel fluorocarbene species, trans-[Mo(η5- C5H5)-(CO)2(CF2)F], corresponding to α-F elimination is observed for the first time. The mechanisms of the various photolysis steps are discussed in relation to the growing chemistry of metal–halogenocarbene complexes.
Databáze:	OpenAIRE
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