01692nas a2200169   4500008004100000245007500041210006900116260000800185300002500193490000600218520110700224100002001331700002201351700002301373700002501396856010101421       2017                        eng d00aIron-based nanocatalyst for the acceptorless dehydrogenation reactions0 aIronbased nanocatalyst for the acceptorless dehydrogenation reac  cDEC  aArticle Number: 21470 v83 aDevelopment of sustainable catalytic systems for fundamentally important synthetic transformations and energy storage applications is an intellectually stimulating challenge. Catalytic dehydrogenation of feedstock chemicals, such as alcohols and amines to value-added products with the concomitant generation of dihydrogen is of much interest in the context of hydrogen economy and is an effective alternative to the classical oxidation reactions. Despite a number of homogeneous catalysts being identified for the acceptorless dehydrogenation, the use of high price and limited availability of precious metals and poor recovery of the catalyst have spurred interest in catalysis with more earth-abundant alternatives, especially iron. However, no report has described a reusable iron-based heterogeneous catalyst for oxidant-free and acceptorless dehydrogenation reactions. Here we replace expensive noble metal catalysts with an inexpensive, benign, and sustainable nanoscale iron catalyst for the efficient acceptorless dehydrogenation of N-heterocycles and alcohols with liberation of hydrogen gas.1 aJaiswal, Garima1 aLandge, Vinod, G.1 aJagadeesan, Dinesh1 aBalaraman, Ekambaram  uhttp://library.ncl.res.in/content/iron-based-nanocatalyst-acceptorless-dehydrogenation-reactions02096nas a2200169   4500008004100000245010400041210006900145260000800214300001400222490000600236520146300242100002501705700003001730700002001760700002101780856012501801       2017                        eng d00aIron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis0 aIroncatalyzed dehydrogenation reactions and their applications i  cAUG  a3177-31950 v73 aInspired by nature, chemists have designed new catalysts in the pursuit of selective bond activation and chemical transformations. Emergent biological systems often use earth-abundant first-row transition elements as catalytically active sites to facilitate specific and highly selective chemical processes. The design of a new catalytic system based on abundant and inexpensive catalysts, particularly the iron-based catalysts, for fundamentally significant synthetic transformations under environmentally benign conditions is an important paradigm in chemical synthesis. In recent times, iron-based catalytic systems have shown unprecedented reactivity in the acceptorless dehydrogenation reactions of feedstock chemicals, with the liberation of molecular hydrogen as the by-product, and have enabled greener chemical synthetic methods and alternative energy storage systems. Indeed, it has been demonstrated that the proper design of iron catalysts by judiciously choosing ligands, can aid in the development of new sustainable energy storage systems and catalysis. This tutorial review focuses on the recent development of iron-based dehydrogenation reactions of fundamentally important feedstock, as a route to sustainable chemical synthesis and energy storage applications. The emerging area of the iron-based dehydrogenation strategy provides an opportunity to make industrially applicable, cost-effective and environmentally benign catalytic systems.1 aBalaraman, Ekambaram1 aNandakumar, Avanashiappan1 aJaiswal, Garima1 aSahoo, Manoj, K.  uhttp://library.ncl.res.in/content/iron-catalyzed-dehydrogenation-reactions-and-their-applications-sustainable-energy-and01329nas a2200205   4500008004100000022001400041245006100055210005900116260000900175300001400184490000700198520069300205100002200898700001700920700001800937700002600955700002500981700002501006856009201031       2020                        eng d  a0022-326300aIron-catalyzed direct julia-type olefination of alcohols0 aIroncatalyzed direct juliatype olefination of alcohols  cAUG   a9876-98860 v853 a<p>Herein, we report an iron-catalyzed, convenient, and expedient strategy for the synthesis of styrene and naphthalene derivatives with the liberation of dihydrogen. The use of a catalyst derived from an earth-abundant metal provides a sustainable strategy to olefins. This method exhibits wide substrate scope (primary and secondary alcohols) functional group tolerance amino, nitro, halo, alkoxy, thiomethoxy, and S- and N-heterocyclic compounds) that can be scaled up. The unprecedented synthesis of 1-methyl naphthalenes proceeds via tandem methenylation/double dehydrogenation. Mechanistic study shows that the cleavage of the C-H bond of alcohol is the rate-determining step.</p>
1 aLandge, Vinod, G.1 aBabu, Reshma1 aYadav, Vinita1 aSubaramanian, Murugan1 aGupta, Virendrakumar1 aBalaraman, Ekambaram  uhttp://library.ncl.res.in/content/iron-catalyzed-direct-julia-type-olefination-alcohols02145nas a2200289   4500008004100000022001400041245013400055210006900189260000900258300001200267490000700279520117400286653000801460653001101468653003001479653002301509653002801532100001501560700001901575700002101594700002601615700002501641700002701666700001701693700002301710856012201733       2021                        eng d  a1867-388000aInsights into the nature of self-extinguishing external donors for ziegler-natta catalysis: a combined experimental and DFT study0 aInsights into the nature of selfextinguishing external donors fo  cJAN   a674-6810 v133 a<p>Developing donors for Ziegler-Natta (ZN) catalysis to control the polymerization reaction and produce polymers with desirable properties has always been challenging due to the multi-component nature of the catalytic systems. Here, we have developed a new synthetic protocol for making two external donors, D-1 (2,2,2-trifluoroethyl myristate) and D-2 (2,2,2-trifluoroethyl palmitate) that show self-extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D-1 and D-2 can undergo parallel reactions with aluminum and titanium species present in the system to produce ketones and aldehydes, which are poisons for ZN catalytic systems, thus explaining their self-extinguishing nature. The non-covalent interaction between the long alkyl chain of the donors with the surface plays a vital role in determining the donors ` self-extinguishing nature. There is a significant thermodynamic preference for the binding of the donor with the longer alkyl chain at the titanium center. The current work, therefore, provides interesting insights into how self-extinguishing donors function in ZN catalytic systems.</p>
10aDFT10adonors10anon-covalent interactions10aself-extinguishing10aZiegler-Natta catalysis1 aRaj, Vipin1 aKumawat, Jugal1 aDhamaniya, Sunil1 aSubaramanian, Murugan1 aBalaraman, Ekambaram1 aGupta, Virendra, Kumar1 aVanka, Kumar1 aGrubbs, Robert, H.  uhttp://library.ncl.res.in/content/insights-nature-self-extinguishing-external-donors-ziegler-natta-catalysis-combined