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Jagannathan, Jake R.; Diemoz, Kayla M.; Targos, Karina; Fettinger, James C.; Franz, Annaliese K.
Chemistry : a European journal, November 22, 2019, Letnik: 25, Številka: 65Journal Article
The catalytic activity, kinetics, and quantification of H‐bonding ability of incompletely condensed polyhedral oligomeric silsesquioxane (POSS) silanols are reported. POSS‐triols, a homogeneous model for vicinal silica surface sites, exhibit enhanced H‐bonding compared with other silanols and alcohols as quantified using a 31P NMR probe. Evaluation of a Friedel–Crafts addition reaction shows that phenyl‐POSS‐triol is active as an H‐bond donor catalyst whereas other POSS silanols studied are not. An in‐depth kinetic study (using RPKA and VTNA) highlights the concentration‐dependent H‐bonding behavior of POSS‐triols, which is attributed to intermolecular association forming an off‐cycle dimeric species. Binding constants provide additional support for reduced H‐bond ability at higher concentrations, which is attributed to competitive association. POSS‐triol self‐association disrupts H‐bond donor abilities relevant for catalysis by reducing the concentration of active monomeric catalyst. Elucidating the POSSible activity: The catalytic activity, kinetics, and quantification of H‐bonding ability of incompletely condensed polyhedral oligomeric silsesquioxane (POSS) silanols are reported. Evaluation of a Friedel–Crafts addition reaction shows that phenyl‐POSS‐triol is active as an H‐bond donor catalyst whereas other POSS silanols studied are not. Kinetic studies were carried out to highlight the concentration‐dependent H‐bonding behavior of POSS‐triols.
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JCR | SNIP | JCR | SNIP | JCR | SNIP | JCR | SNIP |
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