Study of the Reactive Cationic Intermediates in the Gas Phase

Study of the Reactive Cationic Intermediates in the Gas Phase PDF Author: Yana Sandlers
Publisher:
ISBN:
Category :
Languages : en
Pages : 98

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Study of the Reactive Cationic Intermediates in the Gas Phase

Study of the Reactive Cationic Intermediates in the Gas Phase PDF Author: Yana Sandlers
Publisher:
ISBN:
Category :
Languages : en
Pages : 98

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Reactive Intermediates in the Gas Phase

Reactive Intermediates in the Gas Phase PDF Author: D. W. Setser
Publisher: Elsevier
ISBN: 1483220214
Category : Science
Languages : en
Pages : 369

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Reactive Intermediates in the Gas Phase: Generation and Monitoring covers methods for reactive intermediates in the gas phase. The book discusses the generation and measurement of atom and radical concentrations in flow systems; the high temperature flow tubes, generation and measurement of refractory species; and the electronically excited long-lived states of atoms and diatomic molecules in flow systems. The text also describes the production and detection of reactive species with lasers in static systems; the production of small positive ions in a mass spectrometer; and the discharge-excited rare gas halide lasers. Chemists, physicists, and people working in aerochem laboratories will find the book invaluable.

A Study of the Gas Phase Reactivity of Model Biomolecules with Cationic Electrophiles

A Study of the Gas Phase Reactivity of Model Biomolecules with Cationic Electrophiles PDF Author: Michael Alan Freitas
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Reactive Intermediates

Reactive Intermediates PDF Author: Leonardo S. Santos
Publisher: John Wiley & Sons
ISBN: 9783527628735
Category : Science
Languages : en
Pages : 341

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During the last two decades there has been considerable growth in the development of electrospray ionization mass spectrometry (ESI-MS) as a practical method in the study of reaction mechanisms. This method allows the interception and characterization of key intermediates, either as transient species or as protonated/deprotonated forms of neutral species by API-MS. The outstanding features and advantages of ESI-MS make it one of the most suitable tools for the fast screening of intermediates directly from solution, providing hitherto unavailable chemical information to organic chemists. This monograph provides an overview of the mechanisms involved in ESI-MS, the historical perspectives before looking further in-depth at specific reactions and intermediates. Written by researchers in the field, this book is an unique resource for the understanding of this cutting-edge technique.

Investigating the Chemistry of Reactive Intermediates in the Gas-phase by Mass Spectometry and Density Functional Theory

Investigating the Chemistry of Reactive Intermediates in the Gas-phase by Mass Spectometry and Density Functional Theory PDF Author: Xinping Liu
Publisher:
ISBN:
Category :
Languages : en
Pages : 520

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Generation and Observation of Reactive Intermediates in the Gas Phase and Condensed Media

Generation and Observation of Reactive Intermediates in the Gas Phase and Condensed Media PDF Author: Matthew Jordan Nava
Publisher:
ISBN:
Category :
Languages : en
Pages : 446

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A molecular beam mass spectrometer (MBMS) has been constructed and upgraded with a laser desorption system. MBMS has allowed for the detection of reactive small molecules including but not limited to P2 from P2A2 (where A = anthracene, C14H10), HCP from PPh3(HCP)A and various dialkylamino phosphinidenes from their corresponding dibenzo-7-phosphanorbornadiene precursors by mass spectrometry. In cases where the desired reactive small molecule was not detected, MBMS has provided valuable information as to the degradation processes which may be occurring and has guided molecular precursor development. Through the use of highly sensitive microwave spectroscopic techniques, it was found that H2S and N2O3 react to form the elusive molecule HSNO in the gas phase. HSNO is believed to be a crucial intermediate in biological signaling. Through isotopic labeling studies, an accurate structure of HSNO could be derived and subsequent degradation of the molecule was explored. The hexacarboxamide cryptand mBDCA-5t-H6 was used as a ligand to prepare mono- and bimetallic iron complexes of the formula [Fe2(mBDCA-5t)]2− and [Fe(mBDCA-5t-H3)]−. Both complexes were observed to react reversibly or irreversibly with CO or NO respectively to afford [(FeEO)-Fe(mBDCA-5t)]2- or [FeEO(mBDCA-5t-H3)]− where E = C or N. Treatment of [(FeNO)·Fe(mBDCA-5t)]2− with excess NO resulted in the formation of [Fe2O(mBDCA-5t)]2-, which could be independently prepared by treatment of [Fe2(mBDCA-5t)]2− with the O-atom transfer reagent N-methylmorpholine N-oxide. The chemistry of peroxide dianion, in the form of the encapsulated complex [O2[subset]mBDCA- 5t-H6]2-, has been explored in nonaqueous media. In particular, [O2[subset]mBDCA-5t-H6]2- was demonstrated to react with CO gas at 40 °C over the course of several hours to furnish the encapsulated carbonate cryptate, [CO3[subset]mBDCA-5t-H6]2-. Through labeling studies, it was confirmed that the carbon of the carbonate was derived from CO. Treatment of [O2[subset]mBDCA-5t-H6]2- with CO2 also affords [CO3[subset]mBDCA-5t-H6]2-, but with concomitant oxidation of the solvent. The oxidation of the solvent was found to proceed through the reactive oxidants −O2COOCO2- and HOOCO2- and sheds light on oxidative processes which may be occurring in lithium-air cells. Exposure of solid Li2O2 to gaseous p-benzoquinone results in the formation of a blue coating on Li2O2. This coating was identified as the quinone radical anion Li[p-C6H4O2], which forms via lithium and electron transfer from Li2O2. This charge and ion transfer process results in the conversion of Li2O2 to LiO2, a long-sought intermediate in the lithium-air community.

From Cationic Silver Complexes to Reactive Phosphenium- and Arsenium-intermediates Stabilized by Weakly Coordinating Anions

From Cationic Silver Complexes to Reactive Phosphenium- and Arsenium-intermediates Stabilized by Weakly Coordinating Anions PDF Author: Marcin Gonsior
Publisher: Cuvillier Verlag
ISBN: 3865375839
Category :
Languages : en
Pages : 307

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Fundamental Studies of Reactive Intermediates in Homogeneous Catalysis

Fundamental Studies of Reactive Intermediates in Homogeneous Catalysis PDF Author:
Publisher:
ISBN:
Category :
Languages : en
Pages : 7

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The studies involve dissociation of Fe(CO){sub n}−, Ni(CO){sub n}, and other carbonyl anions; decarboxylation of (CO)4FeCOOH− to form CO2 and (CO)4FeH− in the water gas shift reaction; gas-phase bimolecular reactions of carbonyl anions and O2; reaction of O2 with CpMn(CO)2−; gas-phase chemistry of fullerene anions; and gas-phase thermochemistry of bicarbonate ion, bisulfite ion, and their conjugate acids (sulfonate ion was produced).

The Physical Chemistry of Criegee Intermediates in the Gas Phase

The Physical Chemistry of Criegee Intermediates in the Gas Phase PDF Author:
Publisher:
ISBN:
Category :
Languages : en
Pages : 52

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Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular and bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.

Model Systems in Catalysis

Model Systems in Catalysis PDF Author: Robert Rioux
Publisher: Springer Science & Business Media
ISBN: 0387980490
Category : Science
Languages : en
Pages : 531

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Book Description
This book is an excellent compilation of cutting-edge research in heterogeneous catalysis and related disciplines – surface science, organometallic catalysis, and enzymatic catalysis. In 23 chapters by noted experts, the volume demonstrates varied approaches using model systems and their successes in understanding aspects of heterogeneous catalysis, both metal- and metal oxide-based catalysis in extended single crystal and nanostructured catalytic materials. To truly appreciate the astounding advances of modern heterogeneous catalysis, let us first consider the subject from a historical perspective. Heterogeneous catalysis had its beginnings in England and France with the work of scientists such as Humphrey Davy (1778–1829), Michael Faraday (1791–1867), and Paul Sabatier (1854–1941). Sabatier postulated that surface compounds, si- lar to those familiar in bulk to chemists, were the intermediate species leading to catalytic products. Sabatier proposed, for example, that NiH moieties on a Ni sur- 2 face were able to hydrogenate ethylene, whereas NiH was not. In the USA, Irving Langmuir concluded just the opposite, namely, that chemisorbed surface species are chemically bound to surfaces and are unlike known molecules. These chemisorbed species were the active participants in catalysis. The equilibrium between gas-phase molecules and adsorbed chemisorbed species (yielding an adsorption isotherm) produced a monolayer by simple site-filling kinetics.