26910-95-2Relevant academic research and scientific papers
Electron attachment to pentafluorophenol and pentafluoroaniline via reaction with atomic metal anions
Butson,Mayer
, p. 186 - 191 (2014)
Electron transfer to pentafluorophenol and pentafluoroaniline was effected by their reaction with the metal anions Fe-, Cs-, Rb-, Ag- and Cu-, the latter formed by electrospray ionisation of solutions of the corresponding oxalate salt. Both electron transfer and dissociative electron attachment was observed. The results are compared to a recent electron attachment study to these two molecules by ómarsson et al. Based on the appearance of product ions in our study, clear differences are observed between the two methods of formation of the organic anions. Several reactions due to direct reaction with the metal anions are observed.
Gas-Phase Ambident Reactivity of Monohydrated Enolate Anions
Freriks, Ivo L.,Koning, Leo J. de,Nibbering, Nico M. M.
, p. 5976 - 5979 (1992)
The gas-phase reactions between a series of monohydrated enolate anions and unsaturated perfluorocarbon compounds have been studied using Fourrier transform ion cyclotron resonance (FT-ICR) mass spectrometry.The influence of selective solvation at the oxygen atom on the ambident reactivity of enolate anions in the gas phase is investigated through comparison of the observed product distributions with previously obtained data for the corresponding unsolvated anions.This analysis indicates that probably in order to make the nucleophilic addition reactions energetically accessible the water molecule is vaporized from the reaction complex prior to the addition reaction step.This evaporation of a water molecule from the reaction complex is considered to recover the intrinsic chemical reactivity of the enolate anions which is confirmed by the agreement between the observed amibident chemical behavior of the monohydrated and unsolvated enolate anions.
Gas-phase chemistry of the dimethylaluminum oxide anion, [(CH3)2AlO]-
Damrauer,Krempp
, p. 1353 - 1355 (1990)
Flowing afterglow-selected ion flow tube technology (FA-SIFT) has been used to generate and select [(CH3)2AlO]- (1), whose ion-molecule chemistry has been extensively studied. This ion reacts with several fluoroaromatics t
Gas-Phase Chemistry of the Dimethyaluminum Oxide Ion and Related Aluminum Oxide Ions: Comparison of Reactivity with Siloxide Ions
Damrauer, Robert,Krempp, Mich?ele,Micheal,Gordon
, p. 2393 - 2400 (2007/10/02)
The anion [CH3)2Alo]- (1) has prepared In a flowing afterglow selected ion flow tube (FA-SIFT) by ion selection from the reaction mixture of trimethylaluminum dimer and hydroxide. This unusual ion is quite reactife and has extensively studied. It with halogen-containing compounds of several types, including fluorobenzene, chlorobenzene, bromofluorobenzene, acetyl chloride, and HF, to give {(CHj^AKOHJX] , where X = F, Cl, and Br. Its chemistry with hexafteorabenzene and silicon tetrafluoride has also detailed as have a number of reactions with carboxylic adds, esters, anhydrides, sulfur-containing neutrals, alcohols, water, and ammonia. The dominant reaction pattern of 1 involves six-centered processes which require a relatively acidic hydrogen and a lone pair donor atom in the neutral reactant. In these reactions, ion 1 abstracts a proton as the lone pair atom to aluminum, often with concomitant extrusion of a small, neutral molecule. We have compared the reactifity of 1 with that of [(CH3)3SiO]- and briefly examined other aluminum oiide ions. The kinetics of several reactions as well the thermochemical relationships among some of these ions have studied, Acidity studies coupled with thermochemical analysis establish that the conjugate acid of [A1O]~ is A1OH, not HA1O. Computational studies out to the reaction of trimethylaluminum and hydroxide, and the acidities and of A1OH and HA1O.
Transfer of the Diethoxyphosphoryl Group between Imidazole and Aryloxy Anion Nucleophiles
Ba-Saif, Salem,Williams, Andrew
, p. 2204 - 2209 (2007/10/02)
Rate constans have been measured for reaction of imidazole with aryl diethyl phosphate (k1) and of aryloxy anions with N-(diethoxyphosphoryl)imidazolium ion (k-1) in aqueous solution at 25 deg C; they obey the following linear Broensted equations: log k1 = -1.02pKArOH + 1.83 (n = 6, r = 0.989); log k-1 = 0.85pKArOH - 0.48 (n = 10, r = 0.957).The value of βeq (1.87) obtained from βlg and βnuc supports a previously determined value (1.83) for the transfer of the neutral phosphoryl group from phenolate ion nucleophiles.The pKaof (diethoxyphosphoryl)imidazolium ion is 6.04.The equilibrium constant for reaction of 4-nitrophenyl diethyl phosphate with imidazole is 5.9 x 10-6; in the case of the aryl ester from phenol with pKArOH = 4.34 the equilibrium constant is calculated to be unity.The Broensted βeq data are used to calibrate effective charges derived from previously measured βlg values for attack of nucleophiles at phosphorus bearing phenolate ion leaving groups.
Gas phase anionic ipso substitution reactions of some alkyl phenyl ethers
Kleingeld,Nibbering
, p. 1687 - 1690 (2007/10/02)
It is shown by 18O labelling that phenoxide anions are formed both by an SN2 and a nucleophilic aromatic substitution mechanism in the reaction of OH- with methyl phenyl ether. These mechanisms are of minor importance in the ethyl phenyl ether system where phenoxide anions are generated almost exclusively by an E2 mechanism.
