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• W2018575191 abstract "NEXAFS, variable temperature STM and TPR have been used to study model adsorbates of relevance to heterogeneous chiral hydrogenation on platinum surfaces. In both the presence and absence of co-adsorbed hydrogen, quinoline molecules are uniformly though randomly distributed on Pt {1 1 1} at 300 K. At 350 K, irreversible surface reactions denude the Pt terraces of modified adsorption sites. Under conditions of hydrogen starvation, extensive polymerisation of quinoline occurs. In the presence of hydrogen, polymerisation is accompanied by hydrogenolysis. In both cases, the {1 1 1} terraces are depleted of quinoid-modified adsorption sites. Quinoline lies approximately flat at 300 K ( α ∼15°), bonded to the surface predominantly via the aromatic π system. This adsorption geometry remains largely unaffected by heating to 360 K, although the data suggest that molecular tilt increases somewhat with surface coverage ( α ∼20°). Lepidine exhibits a greater tilt angle than quinoline on Pt {1 1 1} ( α ∼32°), the likely result of steric hindrance due to the substituent at the C4 ′ position––a characteristic that is present in all known efficient chiral modifiers for the reaction of interest. These findings are discussed with respect to the mechanism of chiral induction and the origin of enantioselectivity collapse in the asymmetric hydrogenation of α-ketoesters on Pt catalysts." @default.
• W2018575191 created "2016-06-24" @default.
• W2018575191 creator A5020098885 @default.
• W2018575191 creator A5070802709 @default.
• W2018575191 date "2002-02-01" @default.
• W2018575191 modified "2023-10-13" @default.
• W2018575191 title "The structure and reactivity of quinoline overlayers and the adsorption geometry of lepidine on Pt{111}: model molecules for chiral modifiers in enantioselective hydrogenation" @default.
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• W2018575191 doi "https://doi.org/10.1016/s0039-6028(01)01810-6" @default.
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