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

Journal Article · Wed May 23 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00167a004· OSTI ID:6619905

Cooper, G; Sze, Kong Hung; Brion, C E ^[1]

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1. Univ. of British Columbia, Vancouver (Canada)

Core (inner-shell) and valence-shell electron energy loss spectra of the group VIA hexacarbonyls Cr(CO){sub 6}, Mo(CO){sub 6}, and W(CO){sub 6} are compared with those of free CO and Ni(CO){sub 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 {yields} {pi}{sup *} and 1s {yields} {sigma}{sup *} transitions. For the C 1s {yields} {pi}{sup *} transitions vibrational structure was resolved. 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.

• OSTI ID: 6619905
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:11; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBONYLS
CHROMIUM
DATA
DATA ANALYSIS
ELECTRONIC STRUCTURE
ELEMENTS
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
MOLYBDENUM
NUMERICAL DATA
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
TUNGSTEN