01360nas a2200157 4500008004100000245008600041210006900127260000800196300001600204490000700220520080100227100001801028700001601046700002601062856011401088 2016 eng d00aN-2 activation on Al metal clusters: catalyzing role of BN-doped graphene support0 aN2 activation on Al metal clusters catalyzing role of BNdoped gr cOCT a27721-277270 v183 aThe successful sustenance of life demands an ambient abiotic process for N-2 activation and dissociation. The Bosch-Haber process remains the only abiotic and synthetic means for N-2 activation and its fixation. Metal nanoclusters have been recently reported for activating molecular nitrogen. Interestingly, the metal clusters explored so far for N-2 activation are free clusters and, hence, are practically not applicable by experimental chemists. Using density functional theory (DFT) based methodology, we propose a potential catalytic system for di-nitrogen activation, viz. supported Al clusters. Al clusters supported on BN doped graphene sheets are seen to activate N-2 molecule with a red shift in the N-N stretching frequency up to 874 cm(-1) with activation barriers as low as 1.14 eV.1 aKumar, Deepak1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/n-2-activation-al-metal-clusters-catalyzing-role-bn-doped-graphene-support01871nas a2200289 4500008004100000022001400041245013600055210006900191260000900260300001600269490000700285520090000292653001901192653001901211653002001230653001201250653001401262653001101276653002301287100002801310700002901338700001801367700002401385700002601409700002001435856012601455 2021 eng d a2155-543500aNi(II)-catalyzed intramolecular C-H/C-H oxidative coupling: an efficient route to functionalized cycloindolones and indenoindolones0 aNiIIcatalyzed intramolecular CHCH oxidative coupling an efficien cOCT  a12384-123930 v113 aNickel(II)-catalyzed intramolecular C(sp(2))-H/C(sp(3))-H and C(sp(2))-H/C(sp(2))-H oxidative couplings in indoles are achieved via chelation assistance. These reactions provide access to biologically relevant five- and six-membered substituted cyclopentaindolones, carbazolones, and indenoindolones in high yields and good chemoselectivity employing an air-stable and defined nickel catalyst, (bpy)Ni(OAc)(2). The oxidative cyclizations proceeded either through a six-membered or an unconventional seven-membered nickelacycle. An extensive mechanistic investigation by experiments and theoretical calculations revealed a facile indole's C(2)-H nickelation and a rate-limiting reductive elimination process. This intramolecular oxidative cyclization operates via a probable Ni(II)/Ni(III) pathway involving single-electron oxidation of nickel without the participation of a carbon-based radical.10aC-H activation10acycloindolones10aindenoindolones10aindoles10aMechanism10aNickel10aoxidative coupling1 aAnkade, Shidheshwar, B.1 aSamal, Pragnya, Paramita1 aSoni, Vineeta1 aGonnade, Rajesh, G.1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/niii-catalyzed-intramolecular-c-hc-h-oxidative-coupling-efficient-route-functionalized02742nas a2200145 4500008004100000245013400041210006900175260000800244300001200252490000800264520214400272100002202416700002602438856013202464 2021 eng d00aNitrogen activation to reduction on a recyclable V-SAC/BN-graphene heterocatalyst sifted through dual and multiphilic descriptors0 aNitrogen activation to reduction on a recyclable VSACBNgraphene  cMAY a480-4910 v6003 a

Efficient reduction of nitrogen to ammonia at a minimal cost would require a recherche catalyst tailored by assimilating the inherent electronic and reactive nature of Single Atom Catalysts (SACs) on heteroatom doped-graphene. A full-scale DFT study accounting for disparate descriptions of atomic orbitals and representation of support, has been carried out to identify the most active and recyclable SAC/B-graphene composite as catalyst for Nitrogen Reduction Reaction (NRR). Dual and Multiphilic descriptors derived reactivity pattern of six different metal SACs V, Fe, Ni, Ru, W and Re on periodic and non-periodic paradigms of pristine and BN-pair doped graphene supports, align with the calculated chemisorption efficacy and activation of N2. The enzymatic route of nitrogen reduction on three most ideal metal SACs (V, W and Re) culminates Vanadium SAC, a relatively cheaper metal, anchored on BNring-graphene with an energy barrier of ⩽1.24 eV as a highly active and recyclable catalyst for NRR.

1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/nitrogen-activation-reduction-recyclable-v-sacbn-graphene-heterocatalyst-sifted-through-dual