ROLE OF CHLORINE AND ALKALI PROMOTERS IN ETHYLENE EPOXIDATION OVER SINGLE CRYSTAL SILVER SURFACES.

Experiments with N//2O were carried out with a view to obtaining additional information about the reactivity of oxygen surface species. On clean Ag, N//2O decomposition was found to be an activated process which led exclusively to the deposition of O(a) species. The presence of preadsorbed oxygen or subsurface oxygen served to enhance the deposition rate of O(a). Subsequent dosing with ethylene at 300 K of such an oxygen-populated surface followed by TPR examination showed it to be active for ethylene oxide formation. Control experiments established that adventitious decomposition of N//2O at the reactor walls or specimen supports followed by possible re-absorption of O//2(a) was an entirely negligible process. ) The oxidation activity of N//2O was also investigated at elevated pressures in the batch reactor.

Mechanism And Selectivity In The Epoxidation Of Ethylene Over Silver: The Results Of Single Crystal Measurements

The silver-catalysed oxidation of ethylene has been examined on the (III) face of a single crystal by a combination of electron spectroscopy and kinetic measurements at pressures of up to 50 Torr. The necessary and sufficient conditions for ethylene oxide formation are established, reaction intermediates are identified, kinetic isotope effects are observed and the role of Cs in modifying reaction selectivity is examined. It is shown that surface alkali exhibits opposite effects on the reactions which lead to the further oxidation of ethylene oxide and on the direct combustion of ethylene. © 1984.

Organotitanium and niobium chemistry. I. Structure and reactivity of a titanium ethylene complex. II. Reactivity of decamethyl niobocene derivatives

The synthesis and X-ray diffraction study of bis(pentamethylcyclopentadienyl) ethylene titanium (I) are reported. This complex represents the first example of an isolable ethylene adduct of a group IV metal, a key intermediate in Ziegler-Natta olefin polymerization schemes. While treatment of I with ethylene leads to only traces of polymer after months, I participates in a wide range of stoichiometric and catalytic reactions. These include the catalytic conversion of ethylene specifically to butadiene and ethane and the catalytic isomerization of alkenes. Detailed studies have been carried out on the stoichiometric reactions of I with nitriles and alkynes. At low temperatures, nitriles react to form metallacycloimine species which more slowly undergo a formal 1,3-hydrogen shift to generate metallacycloeneamines. The lowest energy pathway for this rearrangement is an intramolecular hydrogen shift which is sensitive to the steric bulk of the R substituent. The reactions of I with alkynes yield metallacyclopentene complexes with high regioisomer selectivity. Carbonylation of the metallacyclopentene (η-C₅Me₅5)₂TiC(CH₃)=C(CH₃)CH₂ under relatively mild conditions cleanly produces the corresponding cyclopentenone and [C₅(CH₃)₅]₂Ti(CO)₂. Compounds derived from CO₂ and acetaldehyde have also been isolated.

The synthesis and characterization of bis-(η-pentamethylcyclopentadienyl) niobium(III) tetrahydroborate (II) are described and a study of its temperature-dependent proton NMR spectroscopic behavior is reported. The complex is observed to undergo a rapid intramolecular averaging process at elevated temperatures. The free energy of activation, ΔG^≠ = 16.4 ± 0.4 kcal/mol, is calculated. The reinvestigation of a related compound, bis(η-cyclopentadienyl)niobium(III) tetrahydroborate, established ΔG^≠ = 14.6 ± 0.2 kcal/mol for the hydrogen exchange process. The tetrahydroborate complex, II reacts with pyridine and dihydrogen to yield (η-C₅Me₅5)₂NbH₃ (III). The reactivity of III with CO and ethylene is reported.