Matrix isolation studies of some group V1 and group V11 substituted metal carbonyl complexes
Matrix isolation studies of some group V1 and group V11 substituted metal carbonyl complexes
Photoprocesses, both photochemical and photophysical, have been studied for a variety of substituted metal carbonyls of groups VI and VII isolated at low temperature in frozen gas matrices. Infrared spectroscopic evidence, including 13CO labelling and energy-factored force field fitting for CH3Mn(CO)5 and CH 3 MM(CO)4$ is presented to show that on photolysis of RMn(CO)5 (R = CH3, CH0)t complexes at high dilutions in CH4, Ar and CO matrices at 10K, news pecies RMn(CO)4, with the R ligand occupying an equatorial position in a trigonal bipyramid and having C2v symmetry, are produced. The results indicate that CH3Mn(C0)4 is fluxional and are discussed in terms of proposed mechanisms for carbonylation/decarbonylation reactions. Infrared spectroscopic evidence is presented to show that on photolysis of Mn(CO)5X (X = C1, Br, I) complexes in Ar and CH4 matrices at 10K, new coordinatively unsaturated species Mn(C0)4X are produced, with the X ligand occupying an equatorial position in a trigonal bipyramid and having C2v symmetry. The reaction is shown to be reversible. The results are related to the mechanistic pathway for substitution reactions. The photochemistry of W(CO)5L, (L = pyridine, 3-bromopyridine, ammonia, hydrogen sulphide) and M(CO) 5(pyridine), (M = Cr, Mo, W), has been studied in both 'inert' and 'reactive' matrices and it has been shown that photo ejection of L or CO can take place. In many cases either reaction can be promoted with virtual selectivity depending on excitation wavelength. All the reactions are shown to be reversible to a degree. Luminescence spectra have been obtained for M(CO)6, (M = Cr, Mo, W) t and M(CO)5(pyridine), (M = Mo or W) complexes in Ar and CH4 matrices at 1OK for the first time. The results are related to observed photochemical processes occurring under the same conditions.
University of Southampton
1980
McHugh, Terence Michael
(1980)
Matrix isolation studies of some group V1 and group V11 substituted metal carbonyl complexes.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Photoprocesses, both photochemical and photophysical, have been studied for a variety of substituted metal carbonyls of groups VI and VII isolated at low temperature in frozen gas matrices. Infrared spectroscopic evidence, including 13CO labelling and energy-factored force field fitting for CH3Mn(CO)5 and CH 3 MM(CO)4$ is presented to show that on photolysis of RMn(CO)5 (R = CH3, CH0)t complexes at high dilutions in CH4, Ar and CO matrices at 10K, news pecies RMn(CO)4, with the R ligand occupying an equatorial position in a trigonal bipyramid and having C2v symmetry, are produced. The results indicate that CH3Mn(C0)4 is fluxional and are discussed in terms of proposed mechanisms for carbonylation/decarbonylation reactions. Infrared spectroscopic evidence is presented to show that on photolysis of Mn(CO)5X (X = C1, Br, I) complexes in Ar and CH4 matrices at 10K, new coordinatively unsaturated species Mn(C0)4X are produced, with the X ligand occupying an equatorial position in a trigonal bipyramid and having C2v symmetry. The reaction is shown to be reversible. The results are related to the mechanistic pathway for substitution reactions. The photochemistry of W(CO)5L, (L = pyridine, 3-bromopyridine, ammonia, hydrogen sulphide) and M(CO) 5(pyridine), (M = Cr, Mo, W), has been studied in both 'inert' and 'reactive' matrices and it has been shown that photo ejection of L or CO can take place. In many cases either reaction can be promoted with virtual selectivity depending on excitation wavelength. All the reactions are shown to be reversible to a degree. Luminescence spectra have been obtained for M(CO)6, (M = Cr, Mo, W) t and M(CO)5(pyridine), (M = Mo or W) complexes in Ar and CH4 matrices at 1OK for the first time. The results are related to observed photochemical processes occurring under the same conditions.
This record has no associated files available for download.
More information
Published date: 1980
Identifiers
Local EPrints ID: 462596
URI: http://eprints.soton.ac.uk/id/eprint/462596
PURE UUID: 7492274e-ab49-49be-9c26-6453a837cf1d
Catalogue record
Date deposited: 04 Jul 2022 19:30
Last modified: 04 Jul 2022 19:30
Export record
Contributors
Author:
Terence Michael McHugh
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics