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 )

Journal Article · Tue Mar 27 23:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00163a004· OSTI ID:6519495

Lichtenberger, D L; Rai-Chaudhuri, A ^[1]

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1. Univ. of Arizona, Tucson (USA)

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.

• DOE Contract Number: AC02-80ER10746
• OSTI ID: 6519495
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:7; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
COMPLEXES
DATA
DATA ANALYSIS
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
INFORMATION
MANGANESE COMPLEXES
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES