The electronic structure of d{sup 6} metal-acetylides
- Univ. of Arizona, Tucson, AZ (United States)
- Brookhaven National Lab., Upton, NY (United States)
- Australian National Univ., Canberra (Australia)
Gas-phase ultraviolet photoelectron spectroscopy has been used to investigate the electronic structure and bonding interactions of d{sup 6} piano-stool metal-acetylides of the general formulas CpML{sub 2}C{triple_bond} C-R [M = Ru, L = PMe{sub 3}, R = H, Me, {sup t}Bu, C{sub 6}H{sub 5}] and CpML{sub 2}C{triple_bond}C-p-C{sub 6}H{sub 4}-NO{sub 2} [M = Fe, Ru, L = CO; M = Ru, L = PMe{sub 3}]. Previous studies of analogous CpFe(CO){sub 2}C{triple_bond}C-R complexes found that the filled-filled interaction between the metal d electrons and the acetylide {pi} bond electrons dominates the shift of the first valence ionizations, and that backbonding of the metal d electrons into the acetylide {pi}* orbitals is very small. It is found here that the change to the second row transition metal and the substitution of phosphines for the carbonyls makes the metal more electron rich, but does not change the basic description of the metal interaction with the acetylide.
- OSTI ID:
- 560176
- Report Number(s):
- CONF-970443-; TRN: 97:005895-0178
- Resource Relation:
- Conference: 213. national meeting of the American Chemical Society, San Francisco, CA (United States), 13-17 Apr 1997; Other Information: PBD: 1997; Related Information: Is Part Of 213th ACS national meeting; PB: 2904 p.
- Country of Publication:
- United States
- Language:
- English
Similar Records
Metal-acetylide bonding in ([eta][sup 5]-C[sub 5]H[sub 5])Fe(CO)[sub 2]C[triple bond]CR compounds. Measures of metal-d[pi]-acetylide-[pi] interactions from photoelectron spectroscopy
sigma. -acetlyide complexes of rhodium(I), rhodium(II), and rhodium(III). Correlation between electrochemical (E degree prime ) and spectroscopic (. Delta. nu. (C=C)) parameters and d. pi. (metal) yields. pi. * (acetylide) transfer