The acidities of nucleophilic monofluoromethylation reagents: An anomalous α‐fluorine effect

H Zheng, Z Li, J **g, XS Xue… - Angewandte Chemie, 2021‏ - Wiley Online Library
Fluorine incorporation into organic molecules is expected to lower the pKa of neighboring
functionality via its strong electron‐withdrawing effect, and this strategy has been widely …

The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion?–synthesis and first applications

A Billion, M Schorpp, R Feser, M Schmitt, L Eisele… - Dalton …, 2023‏ - pubs.rsc.org
Weakly coordinating anions (WCAs) facilitate the stabilization and isolation of highly reactive
and almost “naked” cations. Alkoxyaluminate-based WCAs such as [Al (OC (CF3) 3) …

Deprotonative C–H Silylation of Functionalized Arenes and Heteroarenes Using Trifluoromethyltrialkylsilane with Fluoride

M Sasaki, Y Kondo - Organic Letters, 2015‏ - ACS Publications
A highly selective C–H silylation reaction of functionalized arenes and heteroarenes was
developed using Ruppert–Prakash reagent (TMSCF3) activated by alkali metal fluoride …

Deprotonative Silylation of Aromatic C–H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride

K Nozawa-Kumada, S Osawa, M Sasaki… - The Journal of …, 2017‏ - ACS Publications
A method for the deprotonative silylation of aromatic C–H bonds has been developed using
trifluoromethyltrimethylsilane (CF3SiMe3, Ruppert–Prakash reagent) and a catalytic amount …

Experimental and DFT Studies of the Electron‐Withdrawing Ability of Perfluoroalkyl (RF) Groups: Electron Affinities of PAH (RF) n Increase Significantly with Increasing …

LK San, SN Spisak, C Dubceac… - … A European Journal, 2018‏ - Wiley Online Library
Two series of aromatic compounds with perfluoroalkyl (RF) groups of increasing length, 1, 3,
5, 7‐naphthalene (RF) 4 and 1, 3, 5, 7, 9‐corannulene (RF) 5, have been prepared and their …

Negative Hyperconjugation versus Electronegativity: Vibrational Spectra of Free Fluorinated Alkoxide Ions in the Gas Phase

J Oomens, G Berden, TH Morton - ChemPhysChem, 2015‏ - Wiley Online Library
CO stretching frequencies of free, gaseous, fluorinated alkoxide ions shift substantially to the
blue, relative to those of corresponding alcohols complexed with ammonia. Free α …

Substituent effects on acidity of aryl‐substituted fluoroalkanes: a computational study

M Mishima, JLM Abboud - Journal of Physical Organic …, 2016‏ - Wiley Online Library
The gas‐phase acidities (GA) of various aryl‐substituted fluoroalkanes, XC6H4CH (R1) R2,
were calculated at the B3LYP/6‐311+ G (d, p)//B3LYP/6‐311+ G (d, p). The acidity values of …

Low‐frequency CH stretch vibrations of free alkoxide ions

J Oomens, G Berden, TH Morton - … Chemie International Edition, 2017‏ - Wiley Online Library
CH stretches in hydrocarbon cations often shift to lower frequencies relative to neutral
molecules, because they do not have sufficient electrons to give every bond an electron pair …

Prediction of Gas‐Phase Acidities of Strong Brønsted Acids by ONIOM Method

H Fukaya, T Ono, T Sonoda, M Mishima - Chemistry‐Methods, 2022‏ - Wiley Online Library
The gas‐phase acidities of very strong neutral Brønsted acids are estimated based on
Gaussian theory and two‐layer ONIOM calculations. Although the calculated gas‐phase …

A natural bond orbital analysis of aryl‐substituted polyfluorinated carbanions: negative hyperconjugation

M Suenaga, K Nakata, JLM Abboud… - Journal of Physical …, 2018‏ - Wiley Online Library
Aryl‐substituted polyfluorinated carbanions, ArCHRf− where Rf= CF3 (1), C2F5 (2), i‐C3F7
(3), and t‐C4F9 (4), were analyzed by means of the natural bond orbital (NBO) theory at the …