Application of the Spherical Harmonic Model to the Study of the Terminal v(CO) Spectra of Transition Metal Carbonyl Clusters

Inorganic Chemistry

Volumn 37, Issue 25, 1998, Pages 6502-6510

  Kettle, S F A ^a   Diana, E ^b   Rossetti, R ^b   Stanghellini, P L ^b  

^a UNIVERSITY OF EAST ANGLIA   (United Kingdom)

^b UNIVERSITY OF TURIN   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000563883     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic9807339     Document Type: Article

References (135)

1. 6, M = Cr, Mo, W, are indistinguishable from the modes of the pure components except that the observed frequencies are a function of the composition of the crystal (Kariuki, D. N.; Kettle, S. F. A. Inorg. Chem. 1978, 17, 141). For this particular example the lowest multipolar coupling is quadrupolar - quadrupolar; the corresponding dipolar - dipolar coupling must be expected to be stronger (but is not directly observable because of the broad bands found in the infrared of the crystals).
2. See, for example: Spectrochim. Acta A 1997, 53, 1039-1364 (Special Issue devoted to ab initio calculation of force fields).
3. Of particular note are the octahedral hexacarbonyls, for which the spectral data available (which includes data from isotopomers) are more than adequate to enable a complete and unambiguous normal coordinate analysis (Jones, L. H.; McDowell, R. S.; Goldblatt, M. Inorg. Chem. 1969, 8, 2349). Here, it is invariably found that the absolute magnitude of the cis coupling between two C=O vibrators is greater than that between the two C-M in the intervening C-M-C unit, although the expected attenuation with separation would lead to the opposite inequality. A through-space contribution to the cis coupling of the two C=O vibrators is indicated. It may well occur for the trans coupling too. In any case, it is to be noted that the coupling between cis C=O's (largely through empty space) is greater than that between trans (where there is a high intervening electron density, the effect of which is metal dependent).
4. 13CO. There will not be a single enriched species but several, differing in the position of the enrichment and therefore in spectroscopic characteristics. It will not be possible to enrich one position selectively. Further, in that each molecular vibration may involve all of the terminal CO groups in a molecule, it is far from clear that the displacements of the frequencies of the singly enriched species from those of the nonenriched will be sufficient to enable their resolution. Increasing the enrichment will lead to a plethora of species, the data from which would surely be incapable of deconvolution. Isotopomeric studies are not expected to be of value.
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