((CH/sub 3/)/sub 5/C/sub 5/)/sub 2/TH(CH/sub 3/)/sub 2/ surface chemistry and catalysis. Direct NMR spectroscopic observation of surface alkylation and ethylene insertion/polymerization on MgCl/sub 2/

Journal Article · Wed Mar 02 04:00:00 EST 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00213a061· OSTI ID:7246813

Hedden, D; Marks, T J

It is well-established that adsorption on inorganic surfaces can dramatically alter the reactivity of organometallic molecules; however, the structural chemistry of the resulting adsorbates is frequently ill-defined. From CPMAS NMR studies of Cp'/sub 2/Th(CH/sub 3/)/sub 2/ (Cp' = eta/sup 5/-(CH/sub 3/)/sub 5/C/sub 5/) on dehydroxylated ..gamma..-alumina (DA), they inferred the transfer of methyl groups to DA surface Lewis acid sites and the formation of less saturated Cp'/sub 2/Th(CH/sub 3/)/sup +/ species with cationic character. Although model studies in solution support much of this chemical/spectroscopic hypothesis, the small percentage ( less than or equal to 4%) of Cp'/sub 2/Th(CH/sub 3/)/sub 2//DA sites highly active for olefin hydrogenation and polymerization renders the connection with catalysis necessarily indirect. Complementary studies with high surface area MgCl/sub 2/, the preferred support for third generation Ziegler-Natta catalysis, are reported which provide the first evidence for the catalytic importance of methylmethide transfer on MgCl/sub 2/ and the first direct spectroscopic observation of the ethylene insertion/polymerization process on a supported catalyst.

• Research Organization: Northwestern Univ., Evanston, IL (USA)
• DOE Contract Number: FG02-86ER13511
• OSTI ID: 7246813
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:5; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
ADSORPTION
ALKALINE EARTH METAL COMPOUNDS
ALKYLATION
CARBON 13
CARBON ISOTOPES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNESIUM CHLORIDES
MAGNESIUM COMPOUNDS
MAGNETIC RESONANCE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RESONANCE
SORPTION
SORPTIVE PROPERTIES
SPECTRA
STABLE ISOTOPES
SURFACE PROPERTIES
THORIUM COMPLEXES