Organorhenium surface and catalytic chemistry: silica-supported alkene metathesis catalysts derived from dodecacarbonyltetrakis(. mu. -hydrido)-tetrahedro-tetrarhenium and tetrakis(tricarbonyl(. mu. -hydroxo)rhenium)

Journal Article · Wed Nov 06 00:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00217a044· OSTI ID:6037917

Kirlin, P S; Gates, B C

Silica-supported (Re(CO)/sub 3/OH)/sub 4/ was formed by direct deposition from solution and, alternatively, by reaction of (H/sub 4/Re/sub 4/(CO)/sub 12/) with adsorbed water, as shown by comparisons of infrared, ultraviolet, and /sup 1/H NMR spectra of the surface and of the complex extracted into tetrahydrofuran. The supported (Re(CO)/sub 3/OH)/sub 4/ is inferred to be hydrogen bonded to surface -OH groups; its chemistry is similar to that of (Re(CO)/sub 3/OH)/sub 4/ in solution, but new reactivity is induced by the surface, with adsorbed (HRe/sub 3/(CO)/sub 14/) being formed from (Re(CO)/sub 3/OH)/sub 4/ (or (H/sub 3/Re/sub 3/(CO)/sub 12/)) in the presence of CO at 150/sup 0/C. The supported (Re(CO)/sub 3/OH)/sub 4/ is the precursor of a highly active and stable catalyst for the metathesis of propene: the activity is associated with a small fraction of the rhenium in a higher oxidation state. The oxidation to form the active species takes place under conditions so mild that more highly oxidized species, which are active for alkene polymerization and coke formation, are not formed, and the catalyst is consequently resistant to deactivation. 38 references, 10 figures, 2 tables.

• Research Organization: Univ. of Delaware, Newark
• OSTI ID: 6037917
• Journal Information: Inorg. Chem.; (United States), Vol. 24:23
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
01 COAL, LIGNITE, AND PEAT
02 PETROLEUM
ORGANOMETALLIC COMPOUNDS
CHEMICAL PREPARATION
DEPOSITION
SURFACE PROPERTIES
PROPYLENE
CHEMICAL REACTIONS
RHENIUM COMPOUNDS
CATALYSIS
CATALYSTS
CHEMICAL BONDS
EXPERIMENTAL DATA
HYDROGEN
INFRARED SPECTRA
NMR SPECTRA
OXIDATION
REACTION INTERMEDIATES
SILICA
ULTRAVIOLET SPECTRA
VALENCE
ALKENES
CHALCOGENIDES
DATA
ELEMENTS
HYDROCARBONS
INFORMATION
MINERALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDE MINERALS
OXIDES
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SILICON COMPOUNDS
SILICON OXIDES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
010403 - Coal & Coal Products- Hydrogenation- (-1987)
020400 - Petroleum- Processing