Electronic structure factors of Si-H bond activation by transition metals. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiCl sub 3 and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiHPh sub 2 (Me = CH sub 3 , Ph = C sub 6 H sub 5 )
Abstract
The valence photoelectron spectra of ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(L)HSiCl{sub 3} and ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(L)HSiHPh{sub 2}, where L is CO or P(CH{sub 3}){sub 3}, are compared to determine the effect of ligand substitution at the metal center on Si-H bond activation. Metal centers that are more electron rich may promote more complete oxidative addition of the Si-H bond to the metal. The shifts in the metal and ligand ionization energies and the relative intensities of ionizations in the He I and He II photoelectron experiments show that the metal in ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(PMe{sub 3})HSiCl{sub 3} is best represented by a formal oxidation state of III (d{sub 4} electron count). This indicates nearly complete oxidative addition of the Si-H bond to the metal center and results in independent Mn-H and Mn-Si bonds. In contrast, the splitting and intensity pattern of the metal-based ionizations of ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(PMe{sub 3})HSiHPh{sub 2} reflect the formal d{sup 6} electron count of a metal corresponding to oxidation state I. The extent of electron charge density shift from the metal to the ligand is also small, as evidenced by the negligible shifts of these ionizations from those of the related ({eta}{supmore »
- Authors:
-
- Univ. of Arizona, Tucson (USA)
- Publication Date:
- OSTI Identifier:
- 6835583
- DOE Contract Number:
- AC02-80ER10746
- Resource Type:
- Journal Article
- Journal Name:
- Inorganic Chemistry; (USA)
- Additional Journal Information:
- Journal Volume: 29:5; Journal ID: ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKANES; ELECTRONIC STRUCTURE; AROMATICS; CARBONYLS; CHLORINE COMPOUNDS; MANGANESE COMPLEXES; ORGANIC PHOSPHORUS COMPOUNDS; SILICON COMPLEXES; CHEMICAL BONDS; EXPERIMENTAL DATA; ORGANOMETALLIC COMPOUNDS; COMPLEXES; DATA; HALOGEN COMPOUNDS; HYDROCARBONS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties
Citation Formats
Lichtenberger, D L, and Rai-Chaudhuri, A. Electronic structure factors of Si-H bond activation by transition metals. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiCl sub 3 and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiHPh sub 2 (Me = CH sub 3 , Ph = C sub 6 H sub 5 ). United States: N. p., 1990.
Web. doi:10.1021/ic00330a015.
Lichtenberger, D L, & Rai-Chaudhuri, A. Electronic structure factors of Si-H bond activation by transition metals. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiCl sub 3 and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiHPh sub 2 (Me = CH sub 3 , Ph = C sub 6 H sub 5 ). United States. https://doi.org/10.1021/ic00330a015
Lichtenberger, D L, and Rai-Chaudhuri, A. 1990.
"Electronic structure factors of Si-H bond activation by transition metals. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiCl sub 3 and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiHPh sub 2 (Me = CH sub 3 , Ph = C sub 6 H sub 5 )". United States. https://doi.org/10.1021/ic00330a015.
@article{osti_6835583,
title = {Electronic structure factors of Si-H bond activation by transition metals. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiCl sub 3 and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO)(PMe sub 3 )HSiHPh sub 2 (Me = CH sub 3 , Ph = C sub 6 H sub 5 )},
author = {Lichtenberger, D L and Rai-Chaudhuri, A},
abstractNote = {The valence photoelectron spectra of ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(L)HSiCl{sub 3} and ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(L)HSiHPh{sub 2}, where L is CO or P(CH{sub 3}){sub 3}, are compared to determine the effect of ligand substitution at the metal center on Si-H bond activation. Metal centers that are more electron rich may promote more complete oxidative addition of the Si-H bond to the metal. The shifts in the metal and ligand ionization energies and the relative intensities of ionizations in the He I and He II photoelectron experiments show that the metal in ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(PMe{sub 3})HSiCl{sub 3} is best represented by a formal oxidation state of III (d{sub 4} electron count). This indicates nearly complete oxidative addition of the Si-H bond to the metal center and results in independent Mn-H and Mn-Si bonds. In contrast, the splitting and intensity pattern of the metal-based ionizations of ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO)(PMe{sub 3})HSiHPh{sub 2} reflect the formal d{sup 6} electron count of a metal corresponding to oxidation state I. The extent of electron charge density shift from the metal to the ligand is also small, as evidenced by the negligible shifts of these ionizations from those of the related ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}(PMe{sub 3}) complex. These observations indicate that the electronic structure of the Si-H interaction with the metal in this complex is in the initial stages of Si-H bond addition to the metal, before oxidative addition has become prevalent. 25 refs., 6 figs., 1 tab.},
doi = {10.1021/ic00330a015},
url = {https://www.osti.gov/biblio/6835583},
journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 29:5,
place = {United States},
year = {Wed Mar 07 00:00:00 EST 1990},
month = {Wed Mar 07 00:00:00 EST 1990}
}