Investigation of metal-d[pi]-butadiynyl-[pi] interactions in ([eta][sup 5]-C[sub 5]H[sub 5])(CO)[sub 2]FeC[triple bond]CC[triple bond]CH using photoelectron spectroscopy

Journal Article · Wed Sep 01 00:00:00 EDT 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00033a025· OSTI ID:5526660

Lichtenberger, D L; Renshaw, S K ^[1]; Wong, A; Tagge, C D ^[2]

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1. Univ. of Arizona, Tucson, AZ (United States)
2. Occidental College, Los Angeles, CA (United States)

The electronic structure of ([eta][sup 5]-C[sub 5]H[sub 5])(CO)[sub 2]FeC[triple bond]CC[triple bond]CH (1) is investigated with gas-phase He I and He II photoelectron spectroscopy (PES). A central issue is the electronic communication from the metal through the poly-yne chain. The spectra show distinct ionization bands (ionizations) that originate from the metal d[sup 6] orbitals, the occupied butadiynl [pi] orbitals, the cyclopentadienyl e[double prime][sub 1] orbitals, and the iron-butadiynyl [sigma] bond. Metal-d[pi]-butadiynyl-[pi] electronic interactions are indicated by the splitting pattern of the iron-based ionizations and from changes in ionization cross sections from He I to He II excitation, which indicate the predominant character of ionizations. The C[triple bond]CC[triple bond]CH (butadiynyl) ligand is best described as a net [pi] donor ligand, and in this case the occupied butadiynyl [pi] orbitals interact with occupied metal d[pi] orbitals in filled/filled type interactions. The mixing between occupied metal d[pi] and butadiynyl [pi] orbitals is extensive, and the [pi] system of 1 can be thought of as a five-centered poly-yne. Results from Fenske-Hall and extended Huckel calculations agree with the information obtained from PES. 21 refs., 5 figs., 2 tabs.

• DOE Contract Number: FG02-86ER13501
• OSTI ID: 5526660
• Journal Information: Organometallics; (United States), Vol. 12:9; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
ELECTRONIC STRUCTURE
IONIZATION
IRON COMPLEXES
ALKYNES
MOLECULAR ORBITAL METHOD
ORGANOMETALLIC COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
CALCULATION METHODS
COMPLEXES
ELECTRON SPECTROSCOPY
HYDROCARBONS
ORGANIC COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties