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

Gas phase nucleation is a ubiquitous phenomenon in planetary atmospheres and technical processes, yet our understanding of it is far from complete. In particular, the enhancement of nucleation by the addition of a more volatile, weakly interacting gaseous species to a nucleating vapor has escaped molecular-level experimental investigation. Here, we use a specially designed experiment to directly measure the chemical composition and the concentration of nucleating clusters in various binary CO2-containing vapors. Our analysis suggests that CO2 essentially catalyzes nucleation of the low vapor pressure component through the formation of transient, hetero-molecular clusters and thus provides alternative pathways for nucleation to proceed more efficiently. This work opens up new avenues for the quantitative assessment of nucleation mechanisms involving transient species in multicomponent vapors.

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

Chemical Physics Letters ◽

10.1016/j.cplett.2006.09.056 ◽

2006 ◽

Vol 431 (4-6) ◽

pp. 223-226 ◽

Cited By ~ 11

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

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

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19981498 ◽

1998 ◽

Vol 63 (9) ◽

pp. 1498-1512 ◽

Cited By ~ 17

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.

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