Double C–H Bond Activation of Hydrocarbons by a Gas Phase Neutral Oxide Cluster: The Importance of Spin State

2013 ◽  
Vol 117 (11) ◽  
pp. 2294-2301 ◽  
Author(s):  
Zhe-Chen Wang ◽  
Shi Yin ◽  
Elliot R. Bernstein
Keyword(s):  
Gas Phase ◽  
Spin State ◽  
Bond Activation ◽  
Oxide Cluster ◽  
Activation Of Hydrocarbons

A New Pathway for Activation of C - C and C - H Bonds by Transition Metals in the Gas Phase

2005 ◽  
Vol 58 (2) ◽  
pp. 82 ◽  
Author(s):  
Dongju Zhang ◽  
Ruoxi Wang ◽  
Rongxiu Zhu
Keyword(s):  
Transition Metals ◽  
Gas Phase ◽  
Density Functional Calculations ◽  
Density Functional ◽  
Bond Activation ◽  
Level Density ◽  
Elimination Mechanism ◽  
Activation Of Hydrocarbons ◽  
High Level ◽  
H2 Elimination

C–H and C–C bond activation of hydrocarbons at metal centres are of fundamental importance in biochemistry, organometallic chemistry, and catalysis. The present work aims to search for novel mechanisms for activation of C–C and C–H bonds by transition metals in the gas phase. Using high-level density functional calculations, we systemically studied the reactions of Ti+, V+, and Fe+ with ethane, and proposed new pathways of C–C and C–H bond activation—concerted activation of C–C and C–H bonds, and 1,2-H2 elimination. These two pathways clearly differ from the general addition–elimination mechanism.

Dissecting transmetalation reactions at the molecular level: C–B versus F–B bond activation in phenyltrifluoroborate silver complexes

2021 ◽  
Vol 50 (4) ◽  
pp. 1496-1506
Author(s):  
Fiona Bathie ◽  
Adam W. E. Stewart ◽  
Allan J. Canty ◽  
Richard A. J. O'Hair
Keyword(s):  
Gas Phase ◽  
Bond Activation ◽  
Molecular Level ◽  
Silver Complexes ◽  
Fundamental Model ◽  
Model Reactions

Gas-phase experiments and computation provide fundamental model reactions for aryl and fluoride transfer between silver and boron centres.

Theoretical investigation of the reactivity in the C–F bond activation of CH3F by Lu+ in the gas phase

2006 ◽  
Vol 431 (4-6) ◽  
pp. 223-226 ◽  
Author(s):  
Ze-Yu Liu ◽  
Yong-Cheng Wang ◽  
Zhi-Yuan Geng ◽  
Xiao-Yan Yang ◽  
Han-Qing Wang
Keyword(s):  
Gas Phase ◽  
Theoretical Investigation ◽  
Bond Activation

Generation and Reactivity of Chromium Fluoride Cations (CrF+n, n = 0-4) in the Gas Phase

1998 ◽  
Vol 63 (9) ◽  
pp. 1498-1512 ◽  
Author(s):  
Ulf Mazurek ◽  
Detlef Schröder ◽  
Helmut Schwarz
Keyword(s):  
Gas Phase ◽  
Bond Activation ◽  
Branching Ratio ◽  
Radical Cations ◽  
Reaction Pathways ◽  
Ion Cyclotron Resonance ◽  
Ion Transfer ◽  
Consistent Picture ◽  
Anion Transfer ◽  
Chain Lengths

Gaseous chromium fluoride monocations CrFn+ (n = 1-4) can be prepared by sequential fluorine-atom transfer from nitrogen trifluoride, NF3, to chromium cation. In addition, formal F- anion transfer to CrFn+ (n = 2-4) to yield the corresponding neutral chromium fluorides CrFn+1 is observed. In conjunction with a re-evaluation of previous data, the present results provide a consistent picture of the thermochemistry of neutral and cationic chromium fluorides. The reactivity of the CrFn+ ions towards alkanes is investigated in a Fourier-transform ion cyclotron resonance mass spectrometer. While "bare" Cr+ does not react with alkanes, the chromium fluoride cations CrFn+ do; CrF3+ and CrF4+ are even capable of activating methane. With both increasing oxidation state of chromium and increasing chain lengths of the alkane, the branching ratio of the possible reaction pathways shifts from homolytic C-H and C-C bond activation to hydride- and methanide-ion transfer to yield carbocations, and finally electron transfer generating hydrocarbon radical cations.

scholarly journals Gas phase infrared spectroscopy of mono- and divanadium oxide cluster cations

2004 ◽  
Vol 120 (14) ◽  
pp. 6461-6470 ◽  
Author(s):  
Knut R. Asmis ◽  
Gerard Meijer ◽  
Mathias Brümmer ◽  
Cristina Kaposta ◽  
Gabriele Santambrogio ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Gas Phase ◽  
Oxide Cluster
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