skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electronic structure control of Si-H bond activation by transition metals. 2. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiPh sub 3 , (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiHPh sub 2 , and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiFPh sub 2 (Ph = C sub 6 H sub 5 )

Abstract

The He I photoelectron spectra of ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}HSiHPh{sub 2}, ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}HSiPh{sub 3}, and ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}HSiFPh{sub 2} (Ph = C{sub 6}H{sub 5}) have been obtained in order to measure the nature and extent of Si-H bond interaction with the transition-metal center in these complexes. The principal electronic structure factors contributing to the addition of the Si-H bond to the transition metal involve the interaction of the Si-H {sigma} and {sigma}* orbitals with the metal. The extent of Si-H {sigma}I interaction with the metal is obtained from the shape and splitting pattern of the metal-based ionization band. The electron distribution between the Si-H bond and the metal is indicated by the relative stabilities of the metal-based and ligand-based ionizations. It is found that the metal-based ionizations of these complexes reflect the formal d{sup 6} electron count at the metal center. Also, the small shifts of the valence ionizations reveal that the extent of electron charge density shift from the metal to the ligand is negligible. These observations show that the electronic structure of the Si-H interaction with the metal is in the initial stages of Si-H bond addition to themore » metal, before oxidative addition has become prevalent.« less

Authors:
;  [1]
  1. Univ. of Arizona, Tucson (USA)
Publication Date:
OSTI Identifier:
6519495
DOE Contract Number:  
AC02-80ER10746
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (USA)
Additional Journal Information:
Journal Volume: 112:7; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ORGANOMETALLIC COMPOUNDS; PHOTOELECTRON SPECTROSCOPY; DATA ANALYSIS; ELECTRONIC STRUCTURE; EXPERIMENTAL DATA; MANGANESE COMPLEXES; MEASURING INSTRUMENTS; MEASURING METHODS; COMPLEXES; DATA; ELECTRON SPECTROSCOPY; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; SPECTROSCOPY; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Lichtenberger, D L, and Rai-Chaudhuri, A. Electronic structure control of Si-H bond activation by transition metals. 2. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiPh sub 3 , (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiHPh sub 2 , and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiFPh sub 2 (Ph = C sub 6 H sub 5 ). United States: N. p., 1990. Web. doi:10.1021/ja00163a004.
Lichtenberger, D L, & Rai-Chaudhuri, A. Electronic structure control of Si-H bond activation by transition metals. 2. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiPh sub 3 , (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiHPh sub 2 , and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiFPh sub 2 (Ph = C sub 6 H sub 5 ). United States. https://doi.org/10.1021/ja00163a004
Lichtenberger, D L, and Rai-Chaudhuri, A. 1990. "Electronic structure control of Si-H bond activation by transition metals. 2. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiPh sub 3 , (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiHPh sub 2 , and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiFPh sub 2 (Ph = C sub 6 H sub 5 )". United States. https://doi.org/10.1021/ja00163a004.
@article{osti_6519495,
title = {Electronic structure control of Si-H bond activation by transition metals. 2. Valence photoelectron spectra of (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiPh sub 3 , (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiHPh sub 2 , and (. eta. sup 5 -C sub 5 H sub 4 CH sub 3 )Mn(CO) sub 2 HSiFPh sub 2 (Ph = C sub 6 H sub 5 )},
author = {Lichtenberger, D L and Rai-Chaudhuri, A},
abstractNote = {The He I photoelectron spectra of ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}HSiHPh{sub 2}, ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}HSiPh{sub 3}, and ({eta}{sup 5}-C{sub 5}H{sub 4}CH{sub 3})Mn(CO){sub 2}HSiFPh{sub 2} (Ph = C{sub 6}H{sub 5}) have been obtained in order to measure the nature and extent of Si-H bond interaction with the transition-metal center in these complexes. The principal electronic structure factors contributing to the addition of the Si-H bond to the transition metal involve the interaction of the Si-H {sigma} and {sigma}* orbitals with the metal. The extent of Si-H {sigma}I interaction with the metal is obtained from the shape and splitting pattern of the metal-based ionization band. The electron distribution between the Si-H bond and the metal is indicated by the relative stabilities of the metal-based and ligand-based ionizations. It is found that the metal-based ionizations of these complexes reflect the formal d{sup 6} electron count at the metal center. Also, the small shifts of the valence ionizations reveal that the extent of electron charge density shift from the metal to the ligand is negligible. These observations show that the electronic structure of the Si-H interaction with the metal is in the initial stages of Si-H bond addition to the metal, before oxidative addition has become prevalent.},
doi = {10.1021/ja00163a004},
url = {https://www.osti.gov/biblio/6519495}, journal = {Journal of the American Chemical Society; (USA)},
issn = {0002-7863},
number = ,
volume = 112:7,
place = {United States},
year = {Wed Mar 28 00:00:00 EST 1990},
month = {Wed Mar 28 00:00:00 EST 1990}
}