Radicals in carbonaceous residue deposited on mordenite from methanol

It is shown that control of the degree of coking can lead to the observation of hyperfine structures in the carbonaceous residues deposited from methanol over mordenite (H-MOR) at temperatures relevant to the conversion of methanol to hydrocarbons. EPR measurements of the catalyst samples at various times on stream have been recorded, with a rich hyperfine splitting pattern observed in the early stages of the reaction. Interpretation of the EPR data with the aid of density functional theoretical calculations has afforded the first definitive assignment of the radical cations formed in high temperature coke. The results detail a shortlist of six species: 2,3/2,6/2,7-dimethylnaphthalenium, 2,3,6-trimethylnaphthalenium, 2,3,6,7-tetramethylnaphthalenium, and anthracenium radical cations whose proton hyperfine splitting profiles match the experimental spectra; 2,3,6,7-tetramethylnaphthalenium showed the best agreement. The observation of these particular isomers of polymethylnaphthalene suggest the formation of more highly branched polyaromatic species is less likely within the confines of the H-MOR 12-membered ring channel. These radicals formed when the catalyst is active may constitute key intermediates in the conversion of methanol to light olefins

High activity cobalt based catalysts for the carbonylation of methanol

[Cp(*)Co(CO)2] in the presence of PEt3 and Mel catalyses the carbonylation of methanol with initial rates up to 44 mol dm-3 h-1 before decaying to a second catalytic phase with rates of 3 mol dm-3 h-1; [CoI(CO)2(PEt3)2], which is trigonal bipyramidal with axial PEt3 ligands, has been isolated from the final reaction solution.</p

Dimethyl Ether Carbonylation to Methyl Acetate over Nanosized Mordenites

Nanosized mordenites were found to show significantly enhanced reaction efficiency in dimethyl ether (DME) carbonylation to methyl acetate (MA) because of a greatly facilitated diffusion process. Copper incorporation into the channels of the nanosized mordenites further promoted the reaction rate, selectivity, and stability. Moreover, upon the addition of a small amount of H-2 (5-19 vol %) to the feed gas, deactivation was suppressed during DME carbonylation, whereas the catalyst stability and rate of formation of MA increased

Coordination and organometallic complexes of iron containing o-phenylenebis(dimethylphosphine) (pdmp). Crystal and molecular structure of [Fe(h2-C2H4)(pdmp)2]

Routes to hydrido- and organo-iron complexes of the bidentate ligand o-phenylenebis(dimethylphosphine), o-C6H4(PMe2)2 (pdmp), have been developed, starting from trans-[FeCl2(pdmp)2]. Reduction of trans-[FeC\2(pdmp)2] with LiAlH4 gives the dihydride, cw-[FeH2(pdmp)2], there being no evidence for an intermediate monohydride [FeHCl(pdmp)2]. Treatment of /ra/w-[FeCl2(pdmp)2] with an excess of methyllithium gives [FeMe2(pdmp)2], isolated as a cis//ra;;s-mixture, the methyl groups of which are cleaved by an excess of HX to give [FeX2(pdmp)2] (X = Cl, Br), predominantly in the form of the c/s-isomers. Other new complexes include [FeCI(Me)(pdmp)2] (m//ra;u-mixture) and [Fe(L)(pdmp)2] [L = CO, T|2-C2H4, n2-C8H8, nM,4-C8H6(SiMe3)2, r]2-C4H6, r|2-PhC2Ph and r|2-MeC2Me]. Treatment of/ra/j.c-[FeCl2(pdmp)2] with sodium-naphthalene generates the hydrido(naphthyl)iron(n) complex [FeH(r(1-CIOH7)(pdmp)2] as a cis/trans-mixlute in tautomeric equilibrium with a zerovalent iron naphthalene complex [Fe(r|2-C,0H8)(pdmp)2]. Single crystal X-ray analysis shows that [Fe(n2-C2H4)(pdmp)2] has a distorted octahedral structure in which the ethylene is twisted by ca. 15° relative to the FeP4 skeleton, probably because of steric effects. In solution the coordinated ethylene rotates about the coordination axis with a free energy of activation ΔCt at 324 K of 67 kJ mol-1, as estimated from variable temperature 'H and 31P NMR spectra. In the cyclooctatetraene complexes [Fe(r|2-C8Hg)(pdmp)2] and [Fe{(nM,4C8H6)(SiMe3)2}(pdmp)2] there is also a lower energy process in which the Fe(pdmp)2 unit migrates between the double bonds of the eight-membered ring. The strong electron-donating ability of the Fe(pdmp)2 fragment is indicated by the low value of v(CO) in [Fe(CO)(pdmp)2], the highly shielded 'H and I3C nuclei of coordinated ethylene in [Fe(n2-C2H4)(pdmp)2], the Fe-C and C=C bond lengths in the Fe-C2H4 unit [2.052(8) and 1.418(10) A, respectively], and the facile reversible protonation of the coordinated ethylene by methanol or ethanol. Treatment of [Fe(n2-C2H4)(pdmp)2] with HBF4-OEt2 gives initially a complex ris-[Fe(BF4)(Et)(pdmp)2], in which the ethyl group may be agostic, and finally râ-[Fe(BF4)2(pdmp)2]. The coordinated BF4 groups of the latter compound are displaced by acetonitrile to give c/5-[Fe(NCMe)2(pdmp)2](BF4)2. The BPh4 salts of the cations [FeBr(NCMe)(pdmp)2]'1' and [Fe(NCMe)2(pdmp)2]2+ have also been isolated as mixtures of cis/trans-isomers from râ-[FeX2(pdmp)2] (X = Cl, Br) and acetonitrile

The Crucible, 057

Presented by Illinois Wesleyan University’s School of Theatre Arts, February 21-26, 2017. The production was directed by Professor Thomas Quinn, and featured scenic designs by Professor Curtis Trout, lighting designs by Sunniva Holmlund ’17, sound designs by Dani Von Helms ’17, and costume designs by Connor Speck ’17. Set in a small Massachusetts town in 1692, Arthur Miller’s classic drama is a partially fictionalized account of the Salem witch trials that occurred during that period. Winning the Tony Award for Best Play in 1953, the piece is regarded as a central work in the canon of American drama