01386nas a2200241   4500008004100000022001400041245008900055210006900144260009500213300001200308490000800320520046100328653002500789653003600814653002800850653003000878100001700908700001800925700003000943700001900973700002600992856012601018       2005                        eng d  a0021-951700aMCM-41-supported platinum carbonyl cluster-derived asymmetric hydrogenation catalyst0 aMCM41supported platinum carbonyl clusterderived asymmetric hydro  a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcJAN  a298-3020 v2293 a<p>Anionic platinum carbonyl cluster has been ion paired with cinchonidium groups that are chemically bound to the surface of MCM-41 and fumed silica. In the hydrogenation of methyl pyruvate or acetophenone the fumed silica-based catalyst gives zero enantioselectivity, but under optimum conditions enantiomeric excesses of &gt;90 and similar to40%, respectively, are obtained with the MCM-41-based catalyst. (C) 2004 Elsevier Inc. All rights reserved.</p>10aasymmetric catalysis10afunctionalized inorganic oxides10ahydrogenation catalysts10aplatinum carbonyl cluster1 aBasu, Susmit1 aPaul, Himadri1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/mcm-41-supported-platinum-carbonyl-cluster-derived-asymmetric-hydrogenation-catalyst-002690nas a2200313   4500008004100000022001400041245011600055210006900171260009500240300001200335490000800347520155000355653003601905653002801941653001101969653003001980653002002010653001802030653000802048100001902056700001702075700001702092700003502109700002702144700003002171700001902201700002602220856013002246       2006                        eng d  a0021-951700aEffect of spacer groups on the performance of MCM-41-supported platinum cluster-derived hydrogenation catalysts0 aEffect of spacer groups on the performance of MCM41supported pla  a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcSEP  a332-3390 v2423 a<p>MCM-41 was functionalized with (EtO)(3)SiCH2Cl, (MeO)(3)SiCH2CH2CH2Cl, and (CH3)Cl2SiCH2Cl. The functionalized materials were characterized by solid-state NMR (CPMAS, Si-29 and C-13) and XPS. The NMR data indicate that three new silicon environments were created by(EtO)(3)SiCH2Cl and (MeO)(3)SiCH2CH2CH2Cl, whereas with (CH3)Cl2SiCH2Cl, two new silicon environments were obtained. XPS results from Si 2p core level and the valence band from the material functionalized by (MeO)(3)Si(CH2)(3)Cl was found to be the same as that of the corresponding fresh catalyst (1a), in contrast to that of the materials functionalized by the other two silane reagents. After further functionalization with triethylamine, these materials were used as inorganic anion exchangers to support the cluster anion [Pt-12(CO)(24)](2-). Solid-state NMR (29Si, C-13, N-15) was used to establish the presence of the quaternary ammonium group in the cluster-supported species. Analogous materials were also created using fumed silica as the support, and all of the cluster-supported materials were tested as catalysts for the hydrogenation of methyl pyruvate, acetophenone, nitrobenzene, benzonitrile, ethylacetoacetate, 4-nitrotoluene, cyclohexanone, allyl alcohol, and styrene. The best activity was obtained for the catalyst that had MCM-41 as the support and chloropropyl as the spacer group. TEM showed that the supports and the spacer groups had observable effects on the platinum crystallite size of the catalysts. (c) 2006 Elsevier Inc. All rights reserved.</p>10afunctionalized inorganic oxides10ahydrogenation catalysts10aMCM-4110aplatinum carbonyl cluster10aSolid-state NMR10aspacer groups10aXPS1 aMaity, Niladri1 aBasu, Susmit1 aMapa, Maitri1 aRajamohanan, Pattuparambil, R.1 aGanapathy, Subramanian1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/effect-spacer-groups-performance-mcm-41-supported-platinum-cluster-derived-hydrogenation-102188nas a2200265   4500008004100000022001400041245012200055210006900177260009500246300001200341490000800353520115600361653004001517653002301557653002601580653002801606653003001634100001701664700001701681700003001698700001801728700001901746700002601765856013101791       2006                        eng d  a0021-951700aMCM-41-supported platinum carbonyl cluster-derived catalysts for asymmetric and nonasymmetric hydrogenation reactions0 aMCM41supported platinum carbonyl clusterderived catalysts for as  a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcAPR  a154-1610 v2393 a<p>Anionic platinum carbonyl Cluster ([Pt-12(CO)(24)](2-)) was ion-paired with the 3-chloropropyltrimethoxysilyl-ammonium group chemically bound to the surface of MCM-41. The materials undergo quick decarbonylation and have been characterized before decarbonylation by IR and UV-vis spectroscopy and after decarbonylation by XPS and TEM. They have been used as catalysts for the hydrogenations of methyl pyruvate, acetophenone, nitrobenzene, benzonitrile, and ethylacetoacetate. The support and the quaternary ammonium groups have significant effects on surface platinum concentration, crystallite size, and observed activity. In the hydrogenation of the prochiral substrates methyl pyruvate or acetophenone, the cinchonidine-based catalyst gives significant enantioselectivity under optimum conditions. A kinetic model that includes an enantioselective product-formation step and a hydrogen pressure-dependent step for the deactivation of the enantioselective sites gives reasonable agreement between predicted and observed enantioselectivity. The model is also in accordance with the XPS and TEM data. (c) 2006 Elsevier Inc. All rights reserved.</p>10aasymmetric/non-asymmetric catalysis10aEnantioselectivity10afunctionalized MCM-4110ahydrogenation catalysts10aplatinum carbonyl cluster1 aBasu, Susmit1 aMapa, Maitri1 aGopinath, Chinnakonda, S.1 aDoble, Mukesh1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/mcm-41-supported-platinum-carbonyl-cluster-derived-catalysts-asymmetric-and-nonasymmetric-101548nas a2200205   4500008004100000022001400041245009600055210006900151260007100220300001400291490000800305520074500313100001901058700003501077700002701112700003001139700001901169700002601188856012801214       2008                        eng d  a1932-744700aMCM-41-supported organometallic-derived nanopalladium as a selective hydrogenation catalyst0 aMCM41supported organometallicderived nanopalladium as a selectiv  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUN  a9428-94330 v1123 a<p>Palladium nanocatalysts have been prepared by anchoring (eta(3)-C(3)H(5))(2)Pd(2)Cl(2) onto dian-tine-functionalized MCM-41 supports followed by reaction with hydrogen under catalytic conditions. The catalyst precursor and used catalyst have been studied by solid-state NMR ((13)C, (29)Si), XPS, and TEM. The organometallic-derived catalyst exhibits the best performance (activity and selectivity) to date toward the selective hydrogenation of industrially relevant o- and m-chloronitrobenzene to the corresponding chloroaniline derivatives and is distinctly superior to 5% Pd/C. Grazing angle XPS studies reveal that conversion of the tethered molecular species to the nanoparticles of palladium produces a core-shell nanostructure.</p>1 aMaity, Niladri1 aRajamohanan, Pattuparambil, R.1 aGanapathy, Subramanian1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/mcm-41-supported-organometallic-derived-nanopalladium-selective-hydrogenation-catalyst-001233nas a2200265   4500008004100000022001400041245010500055210006900160260007300229300001200302490000800314520025000322653002500572653002600597653002800623653001700651653003100668100001900699700001700718700002900735700003000764700001900794700002600813856012800839       2008                        eng d  a0926-860X00aMCM-41-supported ruthenium carbonyl cluster-derived catalysts for asymmetric hydrogenation reactions0 aMCM41supported ruthenium carbonyl clusterderived catalysts for a  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUL  a124-1300 v3443 a<p>{The anionic ruthenium carbonyl cluster [Ru-4(mu-H)(3)(CO)(12)](-) has been ion-paired with (3-chloropropyl)-trimethoxysilyl-cinchonidium or sparteinium groups chemically bound to the surfaces of MCM-41 [(MCM-41-)(-O)(3)SiCH2CH2CH2NR3+Cl-</p>10aasymmetric catalysis10afunctionalized MCM-4110ahydrogenation catalysts10ananocatalyst10aruthenium carbonyl cluster1 aIndra, Arindam1 aBasu, Susmit1 aKulkarni, Dhanashree, G.1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/mcm-41-supported-ruthenium-carbonyl-cluster-derived-catalysts-asymmetric-hydrogenation-002265nas a2200181   4500008004100000022001400041245010000055210006900155260011000224300001200334490000700346520151600353100002101869700003001890700001901920700002601939856011801965       2009                        eng d  a1463-926200aApplications of a high performance platinum nanocatalyst for the oxidation of alcohols in water0 aApplications of a high performance platinum nanocatalyst for the  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcFEB  a554-5610 v113 a<p>Nanoparticles of platinum (NP-Pt), have been synthesized by supporting high nuclearity anionic carbonyl cluster (Chini cluster) on a water soluble anion exchanger, and the performance of this material, 1, as an oxidation catalyst for alcohols in water has been studied. The E-factor for the synthesis of NP-Pt by this method has been calculated and compared with that of other NP-Pt recently reported in the literature. With 1 as a catalyst, oxidations of a variety of primary and secondary alcohols by dioxygen are achieved and high turnover numbers and selectivities are obtained. The performances of 1 in the oxidation of benzyl alcohol and 1-phenylethanol are compared with those of three other platinum catalysts. These are platinum nanoparticles 2 prepared by the hydrogen reduction of [PtCl6](2-) supported on the same water soluble polymer, 5% Pt on carbon, and 5% Pt on alumina, designated as 3 and 4, respectively. 1 has been found to be considerably more active than 2- 4 and also other reported water soluble platinum nanocatalysts. After many turnovers (similar to 1000 and similar to 165 for benzyl alcohol and 1-phenyl ethanol, respectively) partial deactivation (similar to 40%) is observed, but the deactivated catalyst can be fully regenerated by treatment with dihydrogen. The TEM data of fresh, deactivated and regenerated 1 show a correlation between the particle size and activity. A mechanism consistent with this and other experimental observations including XPS data is proposed.</p>1 aMaity, Prasenjit1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/applications-high-performance-platinum-nanocatalyst-oxidation-alcohols-water-001071nas a2200205   4500008004100000022001400041245010800055210006900163260007100232300001400303490000800317520026600325100002100591700001800612700003200630700002400662700001900686700003000705856013000735       2009                        eng d  a1932-744700aMgCl2 center dot 4(CH3)(2)CHOH: a new molecular adduct and super active polymerization catalyst support0 aMgCl2 center dot 4CH32CHOH a new molecular adduct and super acti  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY  a8556-85590 v1133 a<p>A new molecular adduct, MgCl(2 center dot)4(CH3)(2)CHOH, has been synthesized and characterized for structural aspects and demonstrated for super active ethylene polymerization activity with TiCl4 to ultrahigh molecular weight polyethylene in high yield.</p>1 aThushara, K., S.1 aMathew, Renny1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/mgcl2-center-dot-4ch32choh-new-molecular-adduct-and-super-active-polymerization-catalyst-001846nas a2200229   4500008004100000022001400041245015600055210006900211260011000280300001600390490000700406520088500413100002601298700002101324700002001345700001801365700003201383700002401415700001901439700003001458856012801488       2011                        eng d  a1477-922600aMgCl2 center dot 6PhCH(2)OH - a new molecular adduct as support material for ziegler-natta catalyst: synthesis, characterization and catalytic activity0 aMgCl2 center dot 6PhCH2OH a new molecular adduct as support mate  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP  a10936-109440 v403 a<p>Benzyl alcohol has been used to prepare a single phase MgCl2 center dot 6BzOH molecular adduct as a support for an ethylene polymerization catalyst (Ziegler catalyst). The structural, spectroscopic and morphological aspects of the MgCl2 center dot 6BzOH molecular adduct and the Ziegler catalyst have been thoroughly studied by various physicochemical characterization techniques. The presence of MgO6 octahedrons due to the interaction of Mg2+ with six -OH groups of the benzyl alcohol is confirmed from a Raman feature at 703 cm(-1), and structural studies. The supported catalyst activity has been evaluated for the ethylene polymerization reaction. The lower polymerization activity of the titanated Ziegler-Natta catalyst compared with a standard catalyst is attributed to the strong interaction of titanium chloride with the support and associated electronic factors.</p>1 aGnanakumar, Edwin, S.1 aThushara, K., S.1 aBhange, Deu, S.1 aMathew, Renny1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/mgcl2-center-dot-6phch2oh-new-molecular-adduct-support-material-ziegler-natta-catalyst-001985nas a2200253   4500008004100000022001400041245011600055210006900171260007300240300001200313490000800325520103000333653002401363653002401387653002701411653001101438653002801449100001901477700003501496700003001531700001901561700002601580856012501606       2011                        eng d  a0926-860X00aSelective hydrogenation of chloronitrobenzenes with an MCM-41 supported platinum allyl complex derived catalyst0 aSelective hydrogenation of chloronitrobenzenes with an MCM41 sup  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAY  a117-1250 v3993 a<p>A platinuin precatalyst (1) has been prepared by reacting [(eta(3)-C3H5)(4)Pt4Cl4] with surface functionalized MCM-41 with pendant -(CH2)(3)NH(CH2)(2)NH2 groups. For the hydrogenation of o-, m- and p-chloronitrobenzenes to the corresponding chloroanilines, 1 is found to be a highly active catalyst with good selectivities for them-and p-isomers. Its performance is superior to that of its palladium analogue and far superior to that of commercial (5%) Pt/C or (5%) Pt/Al2O3. Comparison of solid state and solution NMR data and other evidences indicate that on treatment with the functionalized MCM-41 support; [(eta(3)-C3H5)(4)Pt4Cl4] loses the ally! ligand. XPS data show that in the fresh catalyst Pt is present in the 2+ oxidation state. Based on these and analytical data, co-ordination by surface diamine and hydroxo groups to Pt2+ in 1 is suggested. In the used catalyst both Pt2+ and Pt are present but the amount of metallic platinum is similar to 16% of the total. (C) 2011 Elsevier B.V. All rights reserved.</p>10aChloronitrobenzenes10aDehydrohalogenation10aheterogeneous catalyst10aMCM-4110aSelective hydrogenation1 aIndra, Arindam1 aRajamohanan, Pattuparambil, R.1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/selective-hydrogenation-chloronitrobenzenes-mcm-41-supported-platinum-allyl-complex-002024nas a2200253   4500008004100000022001400041245014100055210006900196260007100265300001400336490000800350520104100358100002101399700002601420700001801446700002401464700003201488700002401520700001901544700002601563700001901589700003001608856013201638       2011                        eng d  a1932-744700aToward an understanding of the molecular level properties of ziegler-natta catalyst support with and without the internal electron donor0 aToward an understanding of the molecular level properties of zie  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcFEB  a1952-19600 v1153 a<p>Two Ziegler-Natta catalysts supported on molecular adducts, namely, MgCl2 center dot 6EtOH (ME) and MgCl2 center dot 5EtOH center dot EtOOCPh (Est-ME), have been prepared. A systematic effort has been made to unravel the molecular level structure property relationships of the catalysts and adducts. Ethylbenzoate is an internal electron donor, and its in situ formation through EtOH+PhCOCl coupling is successfully achieved. The above adduct has been treated with TiCl4, and the resultant catalyst (Ti/Est-ME) is evaluated for ethylene polymerization activity. Rand C-13 CP/MAS NMR of Est-ME (Ti/Est-ME) show carbonyl features at 1730 (1680) cm(-1) and 169 (170) delta, respectively, providing direct support for the presence of ester as an integral part. In spite of low surface area, Ti/Est-ME gives higher yield for ethylene polymerization than the one derived from ME. The results indicate that electronic environment is more important than surface area or any other single factor in determining the polymerization activity.</p>1 aThushara, K., S.1 aGnanakumar, Edwin, S.1 aMathew, Renny1 aJha, Ratnesh, Kumar1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aSarma, Krishna1 aPadmanabhan, Sudhakar1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/toward-understanding-molecular-level-properties-ziegler-natta-catalyst-support-and-without-001978nas a2200217   4500008004100000022001400041245013400055210006900189260011000258300001600368490000700384520106800391100002101459700002601480700001801506700003201524700002401556700001901580700003001599856013101629       2012                        eng d  a1477-922600aMgCl2 center dot 4((CH3)(2)CHCH2OH): a new molecular adduct for the preparation of TiClx/MgCl2 catalyst for olefin polymerization0 aMgCl2 center dot 4CH32CHCH2OH a new molecular adduct for the pre  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUL  a11311-113180 v413 a<p>A new molecular adduct of MgCl2 with isobutanol, namely MgCl2 center dot 4((CH3)(2)CHCH2OH) (MgiBOH), has been prepared as a precursor to the supporting material for an olefin polymerization catalyst. The MgiBOH adduct and final titanated Ziegler-Natta catalysts have been thoroughly characterized by powder XRD, thermal analysis, Raman spectroscopy and solid-state NMR for structural and spectroscopy aspects. A peak observed at 712 cm(-1) in the Raman spectra of MgiBOH indicates the characteristic Mg-O-6 breathing mode and the formation of the adduct. The diffraction feature at 2 theta = 7.8 degrees (d = 11.223 angstrom) in the XRD confirms the adduct formation and the layered structure. The aim of the present article is to study how the insertion of a bulky isobutanol moiety affects the structural and electronic properties of the MgCl2 isobutanol molecular adduct. Indeed, the focus of the present study is to explore how the presence of isobutanol, in the initial molecular adduct, influences the final Z-N catalyst properties and its activity.</p>1 aThushara, K., S.1 aGnanakumar, Edwin, S.1 aMathew, Renny1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/mgcl2-center-dot-4ch32chch2oh-new-molecular-adduct-preparation-ticlxmgcl2-catalyst-olefin-002134nas a2200181   4500008004100000022001400041245011000055210006900165260011000234300001400344490000600358520136900364100001901733700003001752700001901782700002601801856012501827       2013                        eng d  a2044-475300aHydroxyapatite supported palladium catalysts for suzuki-miyaura cross-coupling reaction in aqueous medium0 aHydroxyapatite supported palladium catalysts for suzukimiyaura c  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR  a1625-16330 v33 a<p>Supported palladium catalyst 1 has been prepared by the immobilisation of [Pd(COD)Cl-2] (COD = 1,5-cyclooctadiene) on hydroxyapatite. Catalyst 2 has been prepared by subsequent reduction of catalyst 1 with sodium borohydride in ethanol. Under similar reaction conditions, catalyst 1 with Pd2+, is found to be almost five times more active than 2. Using 1 as the catalyst and water as the solvent, reaction conditions for Suzuki-Miyaura cross-coupling reactions have been optimised under aerobic conditions. The best catalytic activities are observed in the presence of potassium carbonate as the base and tetrabutylammonium bromide as a promoter. Catalyst 1 has been tested for catalytic cross-coupling reactions with sixteen different, electronically neutral, electron rich, electron poor and sterically hindered aryl boronic acids, and several different aryl halides including aryl chlorides. More than thousand turnovers and high selectivities to the hetero-coupled products have been observed in most cases. For many substrates the turnovers with 1 are notably more than what has been reported with other supported catalysts in water. The recyclability and scale-up potential of catalyst 1 have been tested and found to be satisfactory. A negligible drop in activity is observed over ten recycles with an accumulated turnover number of similar to 30000.</p>1 aIndra, Arindam1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar  uhttps://library.ncl.res.in/content/hydroxyapatite-supported-palladium-catalysts-suzuki-miyaura-cross-coupling-reaction-0