03185nas a2200229   4500008004100000022001400041245025900055210006900314260007100383300001400454490000700468520220000475100001502675700001302690700001202703700002202715700001902737700002602756700001602782700002602798856013102824       2005                        eng d  a0020-166900aEffect of 2-(2-pyridyl)azole-based ancillary ligands (L1-4) on the electrophilicity of the nitrosyl function in [Ru-II(trpy)(L1-4)(NO)](3+) [trpy=2,2 `: 6 `,2 `'-terpyridine]. synthesis, structures, and spectroscopic, electrochemical, and kinetic aspects0 aEffect of 22pyridylazolebased ancillary ligands L14 on the elect  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY  a3499-35110 v443 a<p>Ruthenium nitrosyl complexes [Ru(trpy)(L1-4)(NO)](3+) (13-16) [trpy = 2,2':6',2"-terpyridine, L-1 = 2-(2-pyridyl)-benzoxazole, L-2 = 2-(2-pyridyl)benzthiazole, L-3 = 2-(2-pyridyl)benzimidazole, L-4 = 1-methyl-2-(2-pyridyl)-1H-benzimidazole] were obtained in a stepwise manner starting from [Ru-II(trpy)(L1-4) (Cl)]ClO4 (1-4) &amp;RARR; [Ru-II(trpy)(L1-4) (H2O)](ClO4)(2) (5-8) &amp;RARR; [Ru-II(trpy)(L1-4) (NO2)ClO4 (9-12) &amp;RARR; [Ru-II(trpy)(L-1,L-2,L-4) (NO)](ClO4)(3) (13, 14, 16)/[Ru-II(trpy)(L-3) (NO)](Cl)(4))(2)(NO3) (15). Crystal structures of 1, 2, 4, 9, 12, 13, 15, and 16 established the stereoretentive nature of the transformation processes. Though the complexes of L1, L3, and L 4 were isolated in the isomeric form A (π-acceptor trpy and azole ring in the equatorial plane and the pyridine and chloride donors in the axial positions), complexes of L 2 preferentially stabilized in form B (trpy and pyridine in the equatorial plane and the azole ring and chloride donors in the axial positions). The v(NO) stretching frequency varied in the range of 1957-1932 cm(-1), 13 &amp;MGT; 14 &amp;MGT; 15 &gt; 16, primarily depending on the electronic aspects of L as well as the isomeric structural forms. The coordinated nitrosyl function underwent successive reductions of [Ru-II-NO+](3+) &amp;RARR; [Ru-II-NO&amp;BULL;](2+) and [Ru-II-NO&amp;BULL;](2+) - [Ru-II-NO-](+), and the first reduction potential follows the order 14 &gt; 13 &amp;MGT; 15 &amp;AP; 16. The nearly axial EPR spectra having nitrogen hyperfine splittings (A &amp;AP; 26 G) at 77 K of 13(-)-16(-) with (g) &amp;AP; 2.0 established that the reduction process is largely centered around the nitrosyl function. Despite an appreciably high v(NO), the complexes were found to be unusually stable even in the aqueous medium. They transformed slowly and only partially into the corresponding nitro derivatives in H2O (k &amp;AP; 10(-4) s(-1) and K = 0.4-3.8). The chloro (1-4), aqua (5-8), and nitro (9-12) derivatives displayed reasonably strong emissions near 700 nm at 77 K (φ = 10(-1)-10(-2)). The aqua derivative 7 was found to interact with the calf thymus and the circular form of p-Bluescript SK DNA.</p>1 aChanda, N.1 aPaul, D.1 aKar, S.1 aMobin, Shaikh, M.1 aDatta, Anindya1 aPuranik, Vedavati, G.1 aRao, K., K.1 aLahiri, Goutam, Kumar  uhttp://library.ncl.res.in/content/effect-2-2-pyridylazole-based-ancillary-ligands-l1-4-electrophilicity-nitrosyl-function-ru-102689nas a2200313   4500008004100000022001400041245011600055210006900171260009500240300001200335490000800347520155000355653003601905653002801941653001101969653003001980653002002010653001802030653000802048100001902056700001702075700001702092700003502109700002702144700003002171700001902201700002602220856012902246       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  uhttp://library.ncl.res.in/content/effect-spacer-groups-performance-mcm-41-supported-platinum-cluster-derived-hydrogenation-1