Matches in SemOpenAlex for { <https://semopenalex.org/work/W3132472277> ?p ?o ?g. }
- W3132472277 endingPage "3025" @default.
- W3132472277 startingPage "3017" @default.
- W3132472277 abstract "The mechanism of anion-catalyzed C–H silylation by R3SiCF3 reagents has been investigated using homogeneous TBAT-initiation, in situ and stopped-flow 19F NMR spectroscopy 2H-KIE, LFER, deuterium-labeled crossover, structure-selectivity quantitation (TMSCF3/TESCF3), carbene trapping, and DFT-calculations. Analysis of the kinetics of reactions of 1,3-difluorobenzenes (2), and the generation of ArSiMe3 and Me3SiF as a function of the concentration of [2], [TMSCF3], and [TBAT], show that a CF3-anionoid is the active intermediate. The CF3-anionoid is reversibly released from siliconate [(CF3)2SiMe3]− and undergoes partitioning through rate-limiting arene deprotonation (1H/2H KIE 9.5) to generate ArSiMe3 (via a transient aryl anionoid) and fluoroform (CF3H), in competition with F-anion transfer to TMSCF3 to generate CF2 and TMSF. The [2]/[TMSCF3] concentration ratio directly and proportionally controls the kinetics of the partition, in favor of C–H deprotonation. Higher concentrations of TBAT and lower concentrations of TMSCF3 lead to faster rates of ArSiMe3 generation. Use of the homologous TESCF3 reagent leads to faster rates of anion catalysis and an increased selectivity toward C–H deprotonation. Perfluoroalkenes, generated in situ from CF2, capture the CF3-anionoid leading to progressive inhibition of the anion-catalysis. Inhibition is suppressed by using a styrene additive to trap the CF2 and the efficiency of the process enhanced by slow-addition of TMSCF3 (1) to maintain a high concentration ratio [2]/[1]." @default.
- W3132472277 created "2021-03-01" @default.
- W3132472277 creator A5004567326 @default.
- W3132472277 creator A5061287555 @default.
- W3132472277 creator A5072768417 @default.
- W3132472277 creator A5084410806 @default.
- W3132472277 creator A5088949088 @default.
- W3132472277 date "2021-02-22" @default.
- W3132472277 modified "2023-10-16" @default.
- W3132472277 title "Mechanism of Anion-Catalyzed C–H Silylation Using TMSCF<sub>3</sub>: Kinetically-Controlled CF<sub>3</sub>-Anionoid Partitioning As a Key Parameter" @default.
- W3132472277 cites W157350801 @default.
- W3132472277 cites W1780587038 @default.
- W3132472277 cites W1969545648 @default.
- W3132472277 cites W1982620456 @default.
- W3132472277 cites W2009568094 @default.
- W3132472277 cites W2020214768 @default.
- W3132472277 cites W2023384391 @default.
- W3132472277 cites W2025174615 @default.
- W3132472277 cites W2031543336 @default.
- W3132472277 cites W2035382144 @default.
- W3132472277 cites W2036117354 @default.
- W3132472277 cites W2048197179 @default.
- W3132472277 cites W2051628038 @default.
- W3132472277 cites W2060231012 @default.
- W3132472277 cites W2074083010 @default.
- W3132472277 cites W2078015776 @default.
- W3132472277 cites W2089381297 @default.
- W3132472277 cites W2096302098 @default.
- W3132472277 cites W2096598788 @default.
- W3132472277 cites W2104891808 @default.
- W3132472277 cites W2108494167 @default.
- W3132472277 cites W2110939537 @default.
- W3132472277 cites W2114918347 @default.
- W3132472277 cites W2115995789 @default.
- W3132472277 cites W2118483975 @default.
- W3132472277 cites W2119269409 @default.
- W3132472277 cites W2121233250 @default.
- W3132472277 cites W2141746128 @default.
- W3132472277 cites W2158205529 @default.
- W3132472277 cites W2169769457 @default.
- W3132472277 cites W2322601277 @default.
- W3132472277 cites W2334919506 @default.
- W3132472277 cites W2463820929 @default.
- W3132472277 cites W2471661098 @default.
- W3132472277 cites W2510090290 @default.
- W3132472277 cites W2536349726 @default.
- W3132472277 cites W2553164779 @default.
- W3132472277 cites W2557501586 @default.
- W3132472277 cites W2561076811 @default.
- W3132472277 cites W2592656554 @default.
- W3132472277 cites W2607331982 @default.
- W3132472277 cites W2730136782 @default.
- W3132472277 cites W2746749697 @default.
- W3132472277 cites W2759119620 @default.
- W3132472277 cites W2766720996 @default.
- W3132472277 cites W2790498027 @default.
- W3132472277 cites W2790844379 @default.
- W3132472277 cites W2884787146 @default.
- W3132472277 cites W2886873330 @default.
- W3132472277 cites W2888021664 @default.
- W3132472277 cites W2888448731 @default.
- W3132472277 cites W2903586229 @default.
- W3132472277 cites W2914449474 @default.
- W3132472277 cites W2918015495 @default.
- W3132472277 cites W2939410349 @default.
- W3132472277 cites W2950209528 @default.
- W3132472277 cites W2950483958 @default.
- W3132472277 cites W2965295746 @default.
- W3132472277 cites W2983234917 @default.
- W3132472277 cites W2986087553 @default.
- W3132472277 cites W2996302702 @default.
- W3132472277 cites W3004328243 @default.
- W3132472277 cites W3009342118 @default.
- W3132472277 cites W3009736788 @default.
- W3132472277 cites W3014715344 @default.
- W3132472277 cites W3044591481 @default.
- W3132472277 cites W3071306231 @default.
- W3132472277 cites W3081129931 @default.
- W3132472277 cites W3099509215 @default.
- W3132472277 cites W4206035026 @default.
- W3132472277 cites W4248327327 @default.
- W3132472277 doi "https://doi.org/10.1021/acscatal.1c00033" @default.
- W3132472277 hasPublicationYear "2021" @default.
- W3132472277 type Work @default.
- W3132472277 sameAs 3132472277 @default.
- W3132472277 citedByCount "10" @default.
- W3132472277 countsByYear W31324722772021 @default.
- W3132472277 countsByYear W31324722772022 @default.
- W3132472277 countsByYear W31324722772023 @default.
- W3132472277 crossrefType "journal-article" @default.
- W3132472277 hasAuthorship W3132472277A5004567326 @default.
- W3132472277 hasAuthorship W3132472277A5061287555 @default.
- W3132472277 hasAuthorship W3132472277A5072768417 @default.
- W3132472277 hasAuthorship W3132472277A5084410806 @default.
- W3132472277 hasAuthorship W3132472277A5088949088 @default.
- W3132472277 hasBestOaLocation W31324722772 @default.
- W3132472277 hasConcept C118629725 @default.
- W3132472277 hasConcept C118792377 @default.