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It is of fundamental importance to transform carbon monoxide (CO) to petrochemical feedstocks and fine chemicals. Many strategies built on the activation of C=O bond by π-back bonding from the transition metal center were developed during the past decades. Herein, a new CO activation method, in which the CO was converted to the active acyl-like metalloradical, [(por)Rh(CO)]* (por = porphyrin), was reported. The reactivity of [(por)Rh(CO)]* and other rhodium porphyrin compounds, such as (por)- RhCHO and (por)RhC(O)NHnPr, and corresponding mechanism studies were conducted experimentally and computationally and inspired the design of a new conversion system featuring 100% atom economy that promotes carbonylation of amines to formamides using porphyrin rhodium(II) metalloradical. Following this radical based pathway, the carbonylations of a series of primary and secondary aliphatic amines were examined, and turnover numbers up to 224 were obtained. [ABSTRACT FROM AUTHOR]

Under the conditions of oxidative gold catalysis, exposure of ethylene to aryl silanes and alcohols generates products of 1,2-oxyarylation. This provides a rare example of a process that allows catalytic differential 1,2-difunctionalization of this feedstock chemical. [ABSTRACT FROM AUTHOR]

Hydrogenations of CO or CO2 are important catalytic reactions as they are interesting alternatives to produce fine chemical feedstock hence avoiding the use of fossil sources. Using monodisperse nanoparticle (NP) catalysts, we have studied the CO/H2 (i.e., Fischer-Tropsch synthesis) and CO2/H2 reactions. Exploiting synchrotron based in situ characterization techniques such as XANES and XPS, we were able to demonstrate that 10 nm Co NPs cannot be reduced at 250 °C while supported on TiO2 or SiO2 and that the complete reduction of cobalt can only be achieved at 450 °C. Interestingly, cobalt oxide performs better than fully reduced cobalt when supported on TiO2. In fact, the catalytic results indicate an enhancement of 10-fold for the CO2/H2 reaction rate and 2-fold for the CO/H2 reaction rate for the Co/TiO2 treated at 250 °C in H2 versus Co/ TiO2 treated at 450 °C. Inversely, the activity of cobalt supported on SiO2 has a higher turnover frequency when cobalt is metallic. The product distributions could be tuned depending on the support and the oxidation state of cobalt. For oxidized cobalt on TiO2, we observed an increase of methane production for the CO2/H2 reaction whereas it is more selective to unsaturated products for the CO/H2 reaction. In situ investigation of the catalysts indicated wetting of the TiO2 support by CoOx and partial encapsulation of metallic Co by TiO2-x. [ABSTRACT FROM AUTHOR]

The regioselective reductive hydration of terminal alkynes using two complementary dual catalytic systems is described. Branched or linear alcohols are obtained in 75–96% yield with ≥25:1 regioselectivity from the same starting materials. The method is compatible with terminal, di-, and trisubstituted alkenes. This reductive hydration constitutes a strategic surrogate to alkene oxyfunctionalization and may be of utility in multistep settings. [ABSTRACT FROM AUTHOR]

As oil supplies dwindle, there is a growing need to develop new routes to chemical intermediates that utilize alternative feedstocks. We report here a synthesis of para-xylene, one of the highest volume chemicals derived from petroleum, using only ethylene as a feedstock. Ethylene is an attractive alternative feedstock, as it can be derived from renewable biomass resources or harnessed from large domestic shale gas deposits. The synthesis relies on the conversion of hexene (from trimerization of ethylene) to 2,4-hexadiene followed by a Diels-Alder reaction with ethylene to form 3,6-dimethylcyclohexene. This monoene is readily dehydrogenated to para-xylene uncontaminated by the ortho and meta isomers. We report here a selective synthesis of para-xylene, uncontaminated by the ortho or meta isomers, using ethylene as the sole feedstock. [ABSTRACT FROM AUTHOR]

We report the mutually exclusive relationship between carbon nanotube (CNT) yield and crystallinity. Growth conditions were optimized for CNT growth yield and crystallinity through sequential tuning of three input variables: growth enhancer level, growth temperature, and carbon feedstock level. This optimization revealed that, regardless of the variety of carbon feedstock and growth enhancer, the optimum conditions for yield and crystallinity differed significantly with yield/crystallinity, preferring lower/higher growth temperatures and higher/lower carbon feedstock levels. This mutual exclusivity stemmed from the inherent limiting mechanisms for each property. [ABSTRACT FROM AUTHOR]

Methanol, ethanol, and i-propanol were converted under methanol-to-gasoline (MTH)-like conditions (400 °C,1-20 bar) over zeolite H-ZSM-5. For methanol and ethanol, the catalyst lifetimes and conversion capacities are comparable, but when i-propanol is used as the reactant, the catalyst lifetime is increased dramatically. In fact, the total conversion capacity (calculated as the total amount of alcohol converted before deactivation in gaIcohol/gzeoIite) is more than 25 times higher for i-propanol compared to the lower alcohols. Furthermore, when i-propanol is used as the reactant, the selectivity toward alkanes and aromatics declines rapidly over time on stream, and at 20 bar of pressure the liquid product mixture consists almost exclusively of C4-C12 alkenes after approximately a third of the full reaction time. This discovery could open a new route to hydrocarbons via i-propanol from syn-gas or biobased feedstocks. [ABSTRACT FROM AUTHOR]

The article presents information on simple alkenes as substitutes for organometallic reagents. Aliphatic terminal alkenes (alpha olefins) are produced in metric megaton amounts each year, and these chemical feedstocks are starting materials for the preparation of many classes of organic compounds. The value-added component of catalytic intermolecular reactions of these alkenes, such as Ziegler-Natta oligomerization, the Heck reaction, and cross-metathesis, is especially high because they convert an inexpensive raw material into a more highly functionalized compound or polymer with concomitant formation of one or more carbon-carbon bonds.