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Article: Core and valence-shell electronic excitation of the group VI transition-metal hexacarbonyls Cr(CO)6, Mo(CO)6, and W(CO)6 by high-resolution electron energy loss spectroscopy

TitleCore and valence-shell electronic excitation of the group VI transition-metal hexacarbonyls Cr(CO)6, Mo(CO)6, and W(CO)6 by high-resolution electron energy loss spectroscopy
Authors
Issue Date1990
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 1990, v. 112 n. 11, p. 4121-4127 How to Cite?
AbstractCore (inner-shell) and valence-shell electron energy loss spectra of the group VIA hexacarbonyls Cr(CO)6, Mo(CO)6, and W(CO)6 are compared with those of free CO and Ni(CO)4 under kinematic conditions where the spectra are dominated by electric dipole transitions. The transition-metal carbonyl inner-shell C 1s and O 1s spectra show some major similarities to those of free CO, and in particular they exhibit intense 1s → π* and 1s → σ* transitions. For the C 1s →* transitions vibrational structure was resolved. This vibrational structure is influenced by metal d →* CO π* back-bonding effects. However, some significant differences also exist between the spectra of the carbonyl complexes and those of free CO, principally due to greater orbital relaxation accompanying creation of a core hole in the transition-metal compounds and the larger number of final states accessible. Tentative assignments are suggested for the hexacarbonyl spectra with the use of molecular orbital energy level and term value considerations. The significance of the results with regard to the strength and nature of metal-CO bonding in transition-metal carbonyl complexes is discussed, and the potential usefulness of inner-shell electron energy loss spectroscopy as a tool for investigating the bonding in transition-metal species in general is assessed.
Persistent Identifierhttp://hdl.handle.net/10722/157234
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123

 

DC FieldValueLanguage
dc.contributor.authorCooper, Gen_US
dc.contributor.authorSze, KHen_US
dc.contributor.authorBrion, CEen_US
dc.date.accessioned2012-08-08T08:48:18Z-
dc.date.available2012-08-08T08:48:18Z-
dc.date.issued1990en_US
dc.identifier.citationJournal Of The American Chemical Society, 1990, v. 112 n. 11, p. 4121-4127en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/157234-
dc.description.abstractCore (inner-shell) and valence-shell electron energy loss spectra of the group VIA hexacarbonyls Cr(CO)6, Mo(CO)6, and W(CO)6 are compared with those of free CO and Ni(CO)4 under kinematic conditions where the spectra are dominated by electric dipole transitions. The transition-metal carbonyl inner-shell C 1s and O 1s spectra show some major similarities to those of free CO, and in particular they exhibit intense 1s → π* and 1s → σ* transitions. For the C 1s →* transitions vibrational structure was resolved. This vibrational structure is influenced by metal d →* CO π* back-bonding effects. However, some significant differences also exist between the spectra of the carbonyl complexes and those of free CO, principally due to greater orbital relaxation accompanying creation of a core hole in the transition-metal compounds and the larger number of final states accessible. Tentative assignments are suggested for the hexacarbonyl spectra with the use of molecular orbital energy level and term value considerations. The significance of the results with regard to the strength and nature of metal-CO bonding in transition-metal carbonyl complexes is discussed, and the potential usefulness of inner-shell electron energy loss spectroscopy as a tool for investigating the bonding in transition-metal species in general is assessed.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.titleCore and valence-shell electronic excitation of the group VI transition-metal hexacarbonyls Cr(CO)6, Mo(CO)6, and W(CO)6 by high-resolution electron energy loss spectroscopyen_US
dc.typeArticleen_US
dc.identifier.emailSze, KH:khsze@hku.hken_US
dc.identifier.authoritySze, KH=rp00785en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.scopuseid_2-s2.0-0007189813en_US
dc.identifier.volume112en_US
dc.identifier.issue11en_US
dc.identifier.spage4121en_US
dc.identifier.epage4127en_US
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridCooper, G=7402356270en_US
dc.identifier.scopusauthoridSze, KH=7006735061en_US
dc.identifier.scopusauthoridBrion, CE=7006196884en_US

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