01429nas a2200289 4500008004100000022001400041245008100055210006300136260000800199490000700207520052100214653002200735653001300757653003100770653001700801653001200818653002800830653002300858653002600881653002500907653002900932100002600961700002000987700001501007700001901022856009801041 2017 eng d a1359-734500aC(sp(3))-F, C(sp(2))-F and C(sp(3))-H bond activation at silicon(II) centers0 aCsp3F Csp2F and Csp3H bond activation at siliconII centers cSEP0 v533 a

Silylene [PhC(NtBu)(2)SiN(SiMe3)(2)] (1) cleaves the C(sp(3))-H and C-F bonds of acetophenone and 1,1,1-trifluoroacetophenone, respectively, under mild conditions. The reaction is initiated via a nucleophilic attack from the oxygen to the silicon atom followed by C-F/H bond cleavage. The scope of C-F bond activation has further been extended with C6F6 and C6F5CF3.

10aBoron triple bond10aC-F Bond10aFluorinated Building-Block10aH Activation10aKetones10aN-heterocyclic carbenes10aOxodative Addition10aPerfluorinated Arenes10aSelective Activation10aTransition-Metal Centers1 aSwamy, V., S. V. S. N1 aParvin, Nasrina1 aRaj, Vipin1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/csp3-f-csp2-f-and-csp3-h-bond-activation-siliconii-centers02884nas a2200301 4500008004100000022001400041245016300055210006900218260000800287300001800295490000800313520181300321653002402134653002002158653001402178653001702192653001202209653002902221653001902250653002802269653003602297653001502333100001602348700002902364700002702393700003002420856013202450 2017 eng d a1932-744700aWater mediated deactivation of Co3O4 naonrods catalyst for CO oxidation and resumption of activity at and above 373 K: electronic structural aspects by NAPPES0 aWater mediated deactivation of Co3O4 naonrods catalyst for CO ox cSEP a20296–203050 v1213 a

The catalytic activity of the Co3O4 nanorods (NRs) for the CO oxidation reaction and the effect of water on the catalytic reaction have been explored with near-ambient pressure photoelectron spectroscopy (NAPPES) and mass spectral analysis. Comparative NAPPES studies have been employed to understand the elucidation of the catalytic reaction pathway and the evolution of various surface species. The results confirm the suppression of the CO oxidation activity on the Co3O4 NRs in the presence of water vapor. Various type of surface species, such as CO(ads), hydroxyl, carbonate, formate, are found to be present on the catalyst surface depending on the reaction conditions. Vibrational features of CO, O-2, and CO, were observed and shift in binding energy of these features under the reaction conditions directly suggests a change in work function of the catalyst surface. Under dry conditions, CO couples with labile 0 atoms to form CO2; however, under wet conditions, CO predominantly interacts with surface OH groups resulting in the formation of carbonate and formate intermediates. In situ studies of oxidation of CO on Co3O4 shows that CO oxidation depends not only on surface Co3+ concentration but also influenced by Co-3/Co' ratio on the catalyst surface. The carbonate was found to be a reaction inhibitor at room temperature; however, it acts as an active intermediate at 375 K and above. Above the boiling point of water, Co3O4 NR surfaces begin to show the oxidation activity even in the presence of water vapor. The intrinsic role of intermediate species was used to derive a possible reaction mechanism under different reaction conditions.

10aAmbinent-temprature10acarbon monoxide10aGas Shift10aH Activation10aIn-situ10aLow-temprature oxidation10aMolecular-beam10aPerformance enhancement10aRay Photoelectron-Spectroscopyu10aThin-films1 aJain, Ruchi1 aReddy, Kasala, Prabhakar1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/water-mediated-deactivation-co3o4-naonrods-catalyst-co-oxidation-and-resumption-activity-and01692nas a2200229 4500008004100000022001400041245011100055210007100166260000800237490000700245520091500252653001701167653001501184653001701199653001401216653001101230653001401241100002401255700002301279700002001302856014001322 2025 eng d a1867-388000aNickel-catalyzed regioselective C―H alkynylation of pyridones and isoquinolinones using alkynyl bromides0 aNickelcatalyzed regioselective C―H alkynylation of pyridones and cJUN0 v173 a

A straightforward and efficient protocol for the regioselective C & horbar;H alkynylation of 2-pyridones and isoquinolinones with bromoalkynes under nickel catalysis is described. The alkynylation reaction is enabled by a simple and inexpensive Ni(OTf)2/tBubpy catalyst system and uses easily accessible bromoalkynes. The protocol demonstrates a broad substrate scope with up to 95% yield (42 examples) and accommodates synthetically valuable functionalities, such as halides, trifluoromethyl, nitrile, ether, thioether, alkyl silanes, and alkene, as well as heteroarene moieties like pyridinyl, furanyl, and thiophenyl. The pyridinyl directing group on alkynylated 2-pyridones can be smoothly removed to give C6-alkynylated free NH-pyridone. Preliminary mechanistic studies suggest that the alkynylation proceeds via a 2e- oxidative addition pathway involving crucial C & horbar;H activation.

10aalkynylation10aC & horbar10aH Activation10aMechanism10aNickel10apyridones1 aVerma, Suryadev, K.1 aPatil, Harshal, R.1 aPunji, Benudhar uhttps://library.ncl.res.in/content/nickel-catalyzed-regioselective-c%E2%80%95h-alkynylation-pyridones-and-isoquinolinones-using-alkynyl