scholarly journals Elementary Rate Processes in the Dissociative CO for C2H4 Substitution Reactions of Organometallic Complexes in the Gas Phase

1988 ◽  
Vol 9 (1-3) ◽  
pp. 63-73
Author(s):  
Steven J. Duray ◽  
Dawn M. Becher ◽  
Edward R. Grant
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Absorption Spectrometry ◽  
Organometallic Complexes ◽  
Chemical Transformations ◽  
Substitution Reactions ◽  
Time Resolved ◽  
Fast Reactions ◽  
Competitive Kinetics ◽  
Rate Processes

Dissociative substitution mechanisms abound in organometallic chemistry. For certain systems, such processes can be isolated in the gas phase, where, as sequences of elementary unimolecular and bimolecular reactions, their kinetics can convey information on fundamental energetics and dynamics of metal-centered chemical transformations. Methods of competitive kinetics, using time-resolved infrared absorption spectrometry, provide relative and absolute rate constants for comparatively fast reactions. Work yielding unimolecular decay and relative bimolecular production rate constants for selected bis- and tris-ethylene complexes of iron and chromium carbonyls is summarized together with a report of new work on the CO-for-C2H4 substitution kinetics of (C2H4)Cr(CO)5.

A kinetic study of the reactions of OH radicals with fluoroethanes. Estimates of C—H bond strengths in fluoroalkanes

1983 ◽  
Vol 61 (5) ◽  
pp. 861-865 ◽  
Author(s):  
Jean-Pierre Martin ◽  
George Paraskevopoulos
Keyword(s):  
Kinetic Study ◽  
Gas Phase ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Oh Radicals ◽  
Bond Dissociation Energies ◽  
Time Resolved ◽  
Dissociation Energies ◽  
Bond Strengths ◽  
Vacuum Uv

A kinetic study of the reactions of OH radicals with a series of fluoroethanes in the gas phase is presented. OH radicals were generated by flash photolysis of H2O vapor in the vacuum uv (λ > 165 nm) and were monitored in absorption by time-resolved attenuation of resonance radiation at 308.15 nm [OH(A2Σ+ → X2Π)]. The following absolute rate constants (in units of 109 cm3mol−1 s−1 at the 95% confidence limit) were determined at [Formula: see text][Formula: see text][Formula: see text][Formula: see text][Formula: see text]From a linear correlation of the present and previously published rate constants with bond dissociation energies, the following quantities (in kcal mol−1 at 298 K) were estimated to be: D(CH3CHF—H) = 96.3 ± 1.5, D(CH2FCHF—H = 98.8 ± 1.0, D(CF3CHF—H) = 103.5 ± 1.0, D(CHF2CF2—H) = 103.0 ± 1.5, and [Formula: see text][Formula: see text]

Kinetics and Rate Constants of Reactions Leading to Hydration of and in Gaseous Oxygen, Argon, and Helium Containing Traces of Water

1972 ◽  
Vol 50 (14) ◽  
pp. 2230-2235 ◽  
Author(s):  
J. D. Payzant ◽  
A. J. Cunningham ◽  
P. Kebarle
Keyword(s):  
High Pressure ◽  
Electron Beam ◽  
Gas Phase ◽  
Mass Spectrometer ◽  
Rate Constants ◽  
Gas Phase Reactions ◽  
Third Order ◽  
Gaseous Oxygen ◽  
Time Resolved ◽  
Pulsed Electron Beam

The rate constants for the forward and reverse components of gas phase reactions:[Formula: see text]were measured with a pulsed electron beam, time resolved detection high pressure mass spectrometer at 300 °K. O2, Ar, and He at pressures from 1–7 Torr were used as third gas M. The forward reactions were found to be third order and the reverse reactions second order. Establishment of the equilibria could also be observed.

Direct Time-Resolved Study of the Gas-Phase Reactions of Germylene with Ethyl- and Diethylgermane:  Absolute Rate Constants, Temperature Dependences, and Mechanism

2007 ◽  
Vol 111 (8) ◽  
pp. 1434-1440 ◽  
Author(s):  
Rosa Becerra ◽  
Sergey E. Boganov ◽  
Mikhail P. Egorov ◽  
Irina V. Krylova ◽  
Oleg M. Nefedov ◽  
...  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Absolute Rate ◽  
Gas Phase Reactions ◽  
Time Resolved ◽  
Temperature Dependences
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