The first example of a catalytically active system for Suzuki-type cross-coupling reactions perfluorinated arenes such as octafluorotoluene and decafluorobiphenyl is presented.

Abstract The use of carbon dioxide (CO 2 ) as a building block in organic synthesis is topic high interest. We here reflect from an industrial perspective, which the approaches may have potential to be applied near future on significant scale. Drawbacks overcome and challenges addressed are also discussed this critical review. This review focuses systems providing atom‐efficiency could competitive other state‐of‐the art syntheses. magnified image

Alcohol and CO: A new process for hydrogenating CO2 to formic acid has been developed. Calorimetric studies were carried out clarify the role of alcohol solvent in catalytic cycle. hydrogenation is only thermodynamically feasible presence hydrogen-bonding solvents. NMR spectroscopy indicates that catalytically active monocarbonyl complexes are formed when highly basic alkyl phosphine used as catalysts. Detailed facts importance specialist readers published ”Supporting Information”. Such...

The NHC-stabilized complex [Ni2(iPr2Im)4(cod)] (1) was isolated in good yield from the reaction of [Ni(cod)2] with 1,3-diisopropylimidazole-2-ylidene (iPr2Im). Compound 1 is a source [Ni(iPr2Im)2] fragment stoichiometric and catalytic transformations. reactions ethylene CO under atmospheric pressure or equimolar amounts diphenylacetylene lead to compounds [Ni(iPr2Im)2(eta2-C2H4)] (2), [Ni(iPr2Im)2(eta2-C2Ph2)] (3), [Ni(iPr2Im)2(CO)2] (4) yields. In all cases readily transferred without...

The reaction of [Ni2((i)Pr2Im)4(COD)] 1a or [Ni((i)Pr2Im)2(eta(2)-C2H4)] 1b with different fluorinated arenes is reported. These reactions occur a high chemo- and regioselectivity. In the case polyfluorinated aromatics type C6F5X such as hexafluorobenzene (X = F) octafluorotoluene CF3), trimethyl(pentafluorophenyl)silane SiMe3), decafluorobiphenyl C6F5) C-F activation regioselectively takes place at bond in para position to X group afford complexes trans-[Ni((i)Pr2Im)2(F)(C6F5)]2,...

The reaction of [Ni(COD)2] with stable N-heterocyclic carbenes R2Im (R2Im = 1,3-di(R)imidazole-2-ylidene; R2 Me2, nPr2, MeiPr, iPr2) affords homoleptic [Ni(Me2Im)3] (1) or dinuclear, COD-bridged complexes the type [Ni2(R2Im)4(COD)] (R2 2; 3; iPr2, 4). Compounds 1−4 are suitable precursors for synthesis [Ni(R2Im)2]-containing in solution, exemplified by CO under atmospheric pressure, equimolar amounts diphenyl acetylene biphenylene to give carbonyl [Ni(R2Im)2(CO)2] 5; 6; 7; 8),...

The asymmetric ruthenium-catalyzed reductive amination employing ammonia and hydrogen to primary amines is described. Here we demonstrate the capability of our catalyst perform a chemo- enantioselective process while using simple gas as reagent, one most attractive industrially relevant nitrogen sources. presence catalytic amount ammonium iodide was essential for obtaining good yields enantioselectivities. mechanism this reaction investigated by DFT found viable pathway that also explains...

The mechanistic course of the amination alcohols with ammonia catalyzed by a structurally modified congener Milstein's well-defined acridine-based PNP-pincer Ru complex has been investigated both experimentally and DFT calculations. Several key intermediates have isolated characterized. detailed analysis series possible catalytic pathways (e.g., without metal-ligand cooperation, inner- outer-sphere mechanisms) leads us to conclude that most favorable pathway for this catalyst does not...

Abstract A highly selective reductive amination of ketones to primary amines with ammonia and hydrogen using a simple ruthenium catalyst has been developed. The protocol described constitutes an efficient direct atom‐economical approach en route α‐methylbenzylamine derivatives in good high yields. presence catalytic amounts aluminum triflate turned out be crucial for achieving conversion towards amines. magnified image

By using silver complexes with bulky ligands such as DavePhos or N-heterocyclic carbenes, propargylic alcohols are smoothly converted CO2 into a unique class of unexplored cyclic alkylidene carbonates. These systems, for the first time, also achieve direct carboxylative cyclization primary alcohols. The silver-DavePhos catalyst is further applied bis-carboxylative propargyl derivatives, thereby providing an effective route to series previously inaccessible and industrially relevant α-alkylidene

Making industry greener: Many principles for the economic production of organic bulk chemicals, syntheses which have potentially highest environmental impact, currently overlap with green chemistry. However, there remain enough challenges in making industrial synthesis even greener while keeping them efficient, requires research and innovative processes. How efficient chemistry can go hand is reflected this Science Voices article.

We have explored the use of chain end segregation as a means controlling properties polymer surface. Thin film blends homopolystyrene (PS) and PS synthesized with low-energy oligotetrafluoroethylene ends (PS-TFE) were studied using neutron reflectivity. The fraction PS-TFE that localizes near surface was found to increase function its concentration in blend. Contact angle measurements indicate corresponding reductions tension due localization TFE ends. For 10% blend 6000 mol wt 3 × 105 PS,...

A general route for the synthesis of novel NHC stabilized nickel bis(silyl) and hydrido silyl complexes is presented. The reaction [Ni(2)((i)Pr(2)Im)(4)(COD)] 1 ((i)Pr(2)Im = 1,3-di-isopropyl-imidazolin-2-ylidene) with hydrosilanes H(n)SiR(4-n) leads to type [Ni((i)Pr(2)Im)(2)(SiH(n-1)R(4-n))(H)] or [Ni((i)Pr(2)Im)(2)(SiH(n-1)R(4-n))(2)].

The unique reactivity of the nickel(0) complex [Ni2(iPr2Im)4(COD)] (1) (iPr2Im = 1,3-di-isopropyl-imidazolin-2-ylidene) towards hydrosilanes in stoichiometric and catalytic reactions is reported. A series nickel hydrido silyl complexes cis-[Ni(iPr2Im)2(H)(SiHn−1R4−n)] (n 1, 2) bis(silyl) cis-[Ni(iPr2Im)2(SiHn−1R4−n)2] 2, 3) were synthesized by 1 with HnSiR4−n, fully characterized X-ray diffraction spectroscopic methods. These are examples where full oxidative addition step hindered. They...

Abstract Chemical recycling provides a promising solution to utilize plastic waste. Here, catalytic hydrogenative depolymerization of polyamide 66 (PA 66) and polyurethane (PU) was developed. The system employed Ru pincer complexes at high temperature (200 °C) in THF solution, even technical‐grade polymers could be hydrogenated with satisfactory yields under these conditions. A comparison the some known heterogeneous catalysts as well catalyst poisoning tests supported homogeneity system....

A method for the synthesis of industrially relevant monomers adipic acid, 1,6-hexanediol (HDO), and 1,6-hexanediamine (HMD) via isomerizing hydroformylation 1,3-butadiene is described. The aldehyde intermediates are protected in situ as acetals to avoid hydrogenation pentanal. Adipic diacetal obtained good yields, first examples conversion toward 1,6-hexanediol, shown.

Chemical recycling, in particular hydrogenative depolymerization, offers a promising way to utilize plastic waste. This report covers the manganese-catalyzed hydrogenation of polyurethane materials corresponding monomeric units. The key success is Mn pincer complex as potent catalyst combination with elevated temperatures (up 200 °C) and appropriate solvents ensure sufficient solubility polymers. A wide range samples varying polyol isocyanate compositions, some which feature significant...

The reactions of the nickel complex [Ni2(iPr2Im)4(COD)] 1 with organonitriles smoothly and irreversibly proceed via intermediates η2-coordinated organonitrile ligands such as [Ni(iPr2Im)2(η2-(CN)-PhCN)] 2 [Ni(iPr2Im)2(η2-(CN)-pTolCN)] 4 to yield aryl cyanide complexes type trans-[Ni(iPr2Im)2(CN)(Ar)] (Ar = Ph 3, pTol 5, 4-CF3C6H46, 2,4-(OMe)2C6H37, 2-C4H3O 8, 2-C5H4N 9). compounds 7, 9 have been structurally characterized. For conversion 3 a free activation enthalpy ΔG‡(328 K) 103.47 ± 0.79...

Abstract The NHC‐stabilized C–F activation product [Ni( i Pr 2 Im) (F)(C 6 F 5 )] ( 1 ) was isolated from the reaction of [Ni(cod) ] with 1,3‐diisopropylimidazol‐2‐ylidene and hexafluorobenzene. Square‐planar (pentafluorophenyl)nickel complexes type (X)(C were obtained by a systematic derivatization . silylated compounds organyllithium led smoothly to replacement fluorido ligand in halogenido, trifluoromethanesulfonato, cyanido, organyl, selenolato, thiolato, hydrido ligands. According these...

Abstract The reaction of [Ni 2 ( i Pr Im) 4 (COD)] 1 ) { Im = 1,3‐bis(isopropyl)imidazolin‐2‐ylidene} with hexafluorobenzene and decafluorobiphenyl results at room temperature in the formation products a C–F bond activation reaction, i.e. [Ni( (F)(C 6 F 5 )] 12 9 ). reactions or equiv. excess dinuclear (stoichiometric ratio nickel/substrate > 2:1) higher temperatures afford complexes consecutive bond‐activation [1,4‐{Ni( (F)} (C 3 [4,4′‐{Ni( 8 Complexes cleanly react THF...

Abstract The synthesis of sodium acrylate through catalytic carboxylation ethylene with CO 2 in the presence a base is reaction high interest. To develop more efficient and sustainable method to access this valuable monomer, we optimized system one‐step homogeneous nickel‐ or palladium‐catalyzed reaction, without need for stoichiometric amounts an additional reducing agent. Suitable nontoxic solvents such as anisole instead previously reported tetrahydrofuran chlorobenzene were found lead...

Abstract The Pd‐catalysed synthesis of sodium acrylate from ethylene and CO 2 in the presence alcoholate bases has been improved significantly. We used amide solvents such as N ‐cyclohexylpyrrolidone or , ‐dibutylformamide to achieve turnover numbers greater than 500 one run, which is significantly higher that systems for this reaction reported previously. For first time, we were able recycle catalyst without any additional regeneration step. With system, it possible use simple easily...

The Suzuki–Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis crop protection-relevant active ingredients water is disclosed.

To transform highly oxygenated molecules such as polyols from biomass into value‐added chemicals, the deoxygenation via deoxydehydration (DODH) is a promising approach. We report catalytic DODH of substrates renewable resources using Cp*ReO3 (1 mol%, TON up to 32) catalyst and hydrogen reductant. Additionally, synthesis Re(V)‐diolates described for tartrates, glycerol erythritol derivatives. These were obtained in 35 – 53% yield mixtures diastereomers. Their characterization was accomplished...