Formation of Gas-Phase Dianions and Distonic Ions as a General Method for the Synthesis of Protected Reactive Intermediates. Energetics of 2,3- and 2,6-Dehydronaphthalene

2000 ◽  
Vol 122 (43) ◽  
pp. 10689-10696 ◽  
Author(s):  
Dana R. Reed ◽  
Michael Hare ◽  
Steven R. Kass
Keyword(s):  
Gas Phase ◽  
Reactive Intermediates ◽  
Distonic Ions ◽  
General Method

Ultrasensitive spectroscopy of ionic reactive intermediates in the gas phase performed with the first coupling of an IR FEL with an FTICR-MS

2003 ◽  
pp. 541-546
Author(s):  
Philippe Maître ◽  
Sophie Le Caër ◽  
Aude Simon ◽  
William Jones ◽  
Joël Lemaire ◽  
...  
Keyword(s):  
Gas Phase ◽  
Reactive Intermediates ◽  
Fticr Ms

scholarly journals Photoelectron spectroscopy of reactive intermediates

1988 ◽  
Vol 324 (1578) ◽  
pp. 197-207 ◽  
Keyword(s):  
Transition Metal ◽  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectrum ◽  
Reactive Intermediates ◽  
Vapour Phase ◽  
Photoelectron Spectra ◽  
Triatomic Molecule ◽  
Recent Developments ◽  
Vanadium Monoxide

Recent developments in the use of photoelectron spectroscopy to study reactive intermediates in the gas phase are reviewed. The information to be derived on low-lying cationic states from such studies is illustrated by considering two diatomic molecules, NCI and PF, and one triatomic molecule, HNO. Also, the use of a transition-metal photoelectron spectrum to interpret the photoelectron spectrum of the corresponding transition-metal oxide is discussed by using the spectra of vanadium and vanadium monoxide as examples. The value of super-heating in high-temperature photoelectron spectroscopy is demonstrated by considering the vapour-phase photoelectron spectra of the monomers and dimers of sodium hydroxide.

scholarly journals The chemistry of amine radical cations produced by visible light photoredox catalysis

2013 ◽  
Vol 9 ◽  
pp. 1977-2001 ◽  
Author(s):  
Jie Hu ◽  
Jiang Wang ◽  
Theresa H Nguyen ◽  
Nan Zheng
Keyword(s):  
Visible Light ◽  
Radical Cations ◽  
Reactive Intermediates ◽  
Visible Light Photocatalysis ◽  
Photoredox Catalysis ◽  
Iminium Ions ◽  
Distonic Ions ◽  
Synthetic Intermediates

Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.

Hydrolytische Bildung von Perchlorsiloxanen / Formation of Chlorosiloxanes by Hydrolysis

1999 ◽  
Vol 54 (5) ◽  
pp. 577-582 ◽  
Author(s):  
Heike Quellhorst ◽  
Andreas Wilkening ◽  
Nicola Söger ◽  
Michael Binnewies
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Reactive Intermediates ◽  
Reaction Products ◽  
Condensation Reactions ◽  
Intramolecular Condensation ◽  
Hydrolysis Reactions

During the reaction of Si2OCl6 with H2O in the gas phase the intermediate Si2OCl5OH has been observed by mass-spectrometry. Reactive intermediates like this are responsible for the formation of higher chlorosilanes by slow hydrolysis reactions of chlorosilanes and -siloxanes. Reaction products of inter- and intramolecular condensation reactions have been observed by GC-MS-methods.

Deuterium kinetic isotope effects on the thermal isomerizations of deuteriocyclopropane to deuterium-labeled propenes

2005 ◽  
Vol 83 (9) ◽  
pp. 1510-1515
Author(s):  
John E Baldwin ◽  
Stephanie R Singer
Keyword(s):  
Key Words ◽  
Gas Phase ◽  
Bond Cleavage ◽  
Isotope Effects ◽  
Reactive Intermediates ◽  
Kinetic Isotope Effects ◽  
Thermal Rearrangement ◽  
Carbon Bond ◽  
Kinetic Isotope ◽  
Carbon Carbon Bond

The gas-phase thermal isomerizations of deuteriocyclopropane to the four possible monodeuterium-labeled propenes have been followed at 435 °C. The observed distribution of products provides estimates of two deuterium kinetic isotope effects, the secondary [Formula: see text] for the carbon–carbon bond cleavage leading to trimethylene diradical reactive intermediates and the primary [Formula: see text] ratio for a [1,2] shift of a hydrogen or deuterium leading from the diradical to a labeled propene. The values determined are [Formula: see text] = 1.09 ± 0.03 and [Formula: see text] = 1.55 ± 0.06. The experimental [Formula: see text] value found agrees well with some, but not all, earlier calculated values and conjectures. Key words: cyclopropane, thermal rearrangement, kinetic isotope effects.

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