Asphaltene oxide promotes a broad range of synthetic transformations

Carbocatalysts, which are catalytically-active materials derived from carbon-rich sources, are attractive alternatives to metal-based analogs. Graphene oxide is a prototypical example and has been successfully employed in a broad range of synthetic transformations. However, its use is accompanied by a number of practical and fundamental drawbacks. For example, graphene oxide undergoes explosive decomposition when subjected to elevated temperatures or microwaves. We found that asphaltene oxide, an oxidized collection of polycyclic aromatic hydrocarbons that are often discarded from petroleum refining processes, effectively overcomes the drawbacks of using graphene oxide in synthetic chemistry and constitutes a new class of carbocatalysts. Here we show that asphaltene oxide may be used to promote a broad range of transformations, including Claisen-Schmidt condensations, C???C cross-couplings, and Fischer indole syntheses, as well as chemical??reactions??which benefit from the use of??microwave reactors

Post-polymerization modification of poly(vinyl ether)s: A Ru-catalyzed oxidative synthesis of poly(vinyl ester)s and poly(propenyl ester)s

Poly(vinyl ester)s were readily prepared via a ruthenium catalyzed C-H oxidation of the corresponding poly(vinyl ether)s under mild conditions. The transformations were efficient and in many cases proceeded without significant chain cleavage. The method was also successfully used to prepare high molecular weight poly(propenyl ester) for the first time as well as a polyester with a relatively high content (>50%) of ??-butyrolactone repeat unit from poly(tetrahydrofuran). The polymeric products were characterized via FT-IR spectroscopy, NMR spectroscopy, gel permeation chromatography, and other techniques.open

Olefin hydroborations with diamidocarbene-BH3 adducts at room temperature

An isolable N,N???-diamidocarbene (DAC) was previously shown to promote the B-H bond activation of various BH3 complexes. The resultant DAC-BH3 adducts facilitated olefin hydroborations under mild conditions and in the absence of exogenous initiators. The substrate scope for such transformations was further explored and is described herein. While organoboranes were obtained in quantitative yields from various terminal and internal olefins, use of the latter substrates resulted in intramolecular ring-expansion of the newly formed DAC-borane adducts.ope

Synthesis and Study of Olefin Metathesis Catalysts Supported by Redox-Switchable Diaminocarbene 3 Ferrocenophanes

A redox-switchable ligand, N,N'-dimethyldiaminocarbene[3]ferrocenophane (5), was synthesized and incorporated into a series of Ir- and Ru-based complexes. Electrochemical and spectroscopic analyses of (5) Ir(CO)(2)Cl (15) revealed that 5 displayed a Tolman electronic parameter value of 2050 cm(-1) in the neutral state and 2061 cm(-1) upon oxidation. Moreover, inspection of X-ray crystallography data recorded for (5) Ir(cis,cis-1,5-cyclooctadiene)Cl (13) revealed that 5 was sterically less bulky (%V-Bur = 28.4) than other known diaminocarbene[3]ferrocenophanes, which facilitated the synthesis of (5)(PPh3)Cl2Ru-(3-phenylindenylid-1-ene) (18). Complex 18 exhibited quasi-reversible electrochemical processes at 0.79 and 0.98 V relative to SCE, which were assigned to the Fe and Ru centers in the complex, respectively, based on UV-vis and electron pair resonance spectroscopic measurements. Adding 2,3-dichloro-5,6-dicyanoquinone over the course of a ring-opening metathesis polymerization of cis, cis-1,5-cyclooctadiene catalyzed by 18 ([monomer](0)/[18](0) = 2500) reduced the corresponding rate constant of the reaction by over an order of magnitude (pre-oxidation: k(obs) = 0.045 s(-1); post-oxidation: k(obs) = 0.0012 s(-1)). Subsequent reduction of the oxidized species using decamethylferrocene restored catalytic activity (post-reduction: k(obs) = up to 0.016 s(-1), depending on when the reductant was added). The difference in the polymerization rates was attributed to the relative donating ability of the redox-active ligand (i.e., strongly donating 5 versus weakly donating 5(+)) which ultimately governed the activity displayed by the corresponding catalyst.U. S. Army Research Office W911NF-09-1-0446Chemistr

Ring Opening Metathesis Polymerization of Cyclic Allenes

The ring opening metathesis polymerization of cyclic allenes is described. Treating the monomers to a Grubbs-type catalyst afforded polymers that featured allenes integrated into their main chains, as confirmed through a range of spectroscopic, chromatographic, and chemical techniques. Acyclic, 1,3-disubstituted allenes were used as chain transfer agents in the aforementioned reactions. These additives not only provided the corresponding end-functionalized polymers but also enabled control over the molecular weights of the polymers produced. The polymers obtained from the ring opening metathesis polymerization reactions were transformed into silyl-containing derivatives using a hydrosilylation-based, post-polymerization modification. A polymerization mechanism was also deduced and proposed to proceed through a process that involved ruthenium vinylidene intermediates and selective chain transfer

Elucidating the electrochemical activity of electrolyte-insoluble polysulfide species in lithium-sulfur batteries

The direct synthesis of Li2 S2 , a proposed solid intermediate in the discharge of lithium-sulfur (Li-S) batteries, was accomplished by treating elemental lithium with sulfur in liquid ammonia at -41?? C. The as-synthesized product was analyzed by X-ray photoelectron spectroscopy (XPS) as well as X-ray diffraction (XRD) and determined to be a mixture of crystalline Li2 S, amorphous Li2 S2, and higher-order polysulfides (Li2 Sx , x > 2). Monitored filtration followed by a tailored electrochemical approach was used to successfully remove the higher-order polysulfides and yielded a powder, which was determined by XPS to be comprised of 9 mol% insoluble polysulfide species (mainly Li2 S2 ) and 91 mol% Li2 S. This material was discharged galvanostatically in an electrochemical cell and, despite the lack of soluble polysulfide species, was shown to exhibit a discharge plateau at 2.1 V vs. Li/Li+ . This result confirmed the electrochemical reducibility of electrolyte-insoluble polysulfides in Li-S batteries. Moreover, it was determined that the reduction of solid polysulfides was confined to areas where the sulfur-sulfur bonds were in intimate contact with the conductive current collector. Finally, it was observed that commercially available Li2 S samples contain significant quantities of polysulfide-type impurities.ope

A Computational Investigation of the Catalytic Properties of Graphene Oxide: Exploring Mechanisms Using DFT Methods

Here we describe a computational study undertaken in an effort to elucidate the reaction mechanisms behind the experimentally observed oxidations and hydrations catalyzed by graphene oxide (GO). Using the oxidation of benzyl alcohol to benzaldehyde as a model reaction, density functional theory (DFT) calculations revealed that this reactivity stemmed from the transfer of hydrogen atoms from the organic molecule to the GO surface. In particular, neighbouring epoxide groups decorating GO's basal plane were ring-opened, resulting in the formation of diols, followed by dehydration. Consistent with the experimentally-observed dependence of this chemistry on molecular oxygen, our calculations revealed that the partially reduced catalyst was able to be recharged by molecular oxygen, allowing for catalyst turnover. Functional group-free carbon materials, such as graphite, were calculated to have substantially higher reaction barriers, indicating that the high chemical potential and rich functionality of GO are necessary for the observed reactivity.Comment: 5 two column pages, 4 figures, stability of reduced graphene oxide also discussed, accepted to ChemCatChe

Atom Transfer Radical Polymerization in the Solid-State

Poly(2-vinylnaphthalene) was synthesized in the solid-state by ball milling a mixture of the corresponding monomer, a Cu-based catalyst, and an activated haloalkane as the polymerization initiator. Various reaction conditions, including milling time, milling frequency and added reductant to accelerate the polymerization were optimized. Monomer conversion and the evolution of polymer molecular weight were monitored over time using H-1 NMR spectroscopy and size exclusion chromatography, respectively, and linear correlations were observed. While the polymer molecular weight was effectively tuned by changing the initial monomer-to-initiator ratio, the experimentally measured values were found to be lower than their theoretical values. The difference was attributed to premature mechanical decomposition and modeled to accurately account for the decrement. Random copolymers of two monomers with orthogonal solubilities, sodium styrene sulfonate and 2-vinylnaphthalene, were also synthesized in the solid-state. Inspection of the data revealed that the solid-state polymerization reaction was controlled, followed a mechanism similar to that described for solution-state atom transfer radical polymerizations, and may be used to prepare polymers that are inaccessible via solution-state methods

A Dual-Fluorescent Composite of Graphene Oxide and Poly(3-Hexylthiophene) Enables the Ratiometric Detection of Amines

A composite prepared by grafting a conjugated polymer, poly(3-hexylthiophene) (P3HT), to the surface of graphene oxide was shown to result in a dual-fluorescent material with tunable photoluminescent properties. Capitalizing on these unique features, a new class of graphene-based sensors that enables the ratiometric fluorescence detection of amine-based pollutants was developed. Moreover, through a detailed spectroscopic study, the origin of the optical properties of the aforementioned composite was studied and was found to be due to electronic decoupling of the conjugated polymer from the GO. The methodology described herein effectively overcomes a long-standing challenge that has prevented graphene based composites from finding utility in sensing and related applications.Meng, Dongli, Shaojun Yang, Dianming Sun, Yi Zeng, Jinhua Sun, Yi Li, Shouke Yan, Yong Huang, Christopher W. Bielawski, and Jianxin Geng. "A dual-fluorescent composite of graphene oxide and poly (3-hexylthiophene) enables the ratiometric detection of amines." Chemical Science 5, no. 8 (Apr., 2014): 3130-3134.Chemistr

Potentiostatically Controlled Olefin Metathesis

A Ru(II) complex supported by an N-heterocyclic carbene annulated to a redox-active naphthoquinone (NQ) was interrogated using a range of potentiodynamic and potentiostatic electrochemical techniques. The complex exhibited two redox processes, one of which was attributed to the Ru(II)IRu(III) couple (E-1/2 = +1.10 V vs a saturated calomel electrode) and the other to the NQJNIQ(-) couple (E-1/2 = -0.62 V). Using potentiostatic coulometry or bulk electrolysis, the application of a fixed negative potential (-0.9S V) to electrodes placed in a dichloromethane solution containing the complex resulted in a reduction reaction. The complex was quantitatively reduced within minutes, as determined by coulometry, and subsequently oxidized to its initial, neutral form through the application of a relatively positive potential (+0.34 V) over similar periods of time. The interconversion process was found to be reversible and used to modulate a series of ring-closing metathesis and ring-opening metathesis polymerization reactions. While relatively high activities were observed when the neutral form of the catalyst was employed, the reaction rates were attenuated upon in situ, potentiostatic reduction. Toggling between relatively negative or positive potentials enabled the aforementioned olefin metathesis reactions to be switched between fast and slow states