Photochemistry of chloro-, bromo-, and iodo-pentacarbonylmanganese in frozen gas matrices at 12 K. Infrared spectroscopic evidence for tetracarbonylhalogenomanganese species with a C 2? trigonal-bipyramidal structure
- 1 January 1980
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 1803-1808
- https://doi.org/10.1039/dt9800001803
Abstract
Infrared spectroscopic evidence, including 13CO labelling and energy-factored force-field fitting for [Mn(CO)5Cl] and [Mn(CO)4Cl], is presented to show that on photolysis of [Mn(CO)5X](X = Cl, Br, or I) complexes at high dilutions in Ar and CH4 matrices at 12 K new species [Mn(CO)4X], with the X ligand occupying an equatorial position in a trigonal-bipyramidal structure and having C2v symmetry, are produced. The observations of CO ejection, the formation of a co-ordinatively unsaturated species, and the reversibility of the reaction (i) are interpreted as [Mn(CO)5X] [graphic omitted] [Mn(CO)4X]+ CO (i) confirming the existence of a co-ordinatively unsaturated species as the intermediate in the substitution reactions of [Mn(CO)5X] complexes; i.e. the reaction follows the dissociative path proposed from previous kinetic studies.Keywords
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