Binding Interaction of the Trimethylsilyl Cation with Oxygen and Nitrogen Bases in the Gas Phase. Acetopheones, Benzaldehydes, Pyridines, Anilines, andN,N-Dimethylanilines

1,3-Dipolar reagents with an unsaturated CNO- or CNN-skeleton undergo 1,3-organoboration by triorganoboranes. On the other hand, the unsaturated NNO-skeletons in azoxybenzene or nitrous-oxide are reduced to the corresponding NN-fragment by trialkylboranes. The 1,3-addition of aminoborane Cl2BNMe2 to the aldimineoxide PhHC = NMe-0 represents one of the rare examples of analogous reactivity of BN- and CC-double bonds. O-Borylhydroxylamines PhHCR-NMe-OBR2 are reduced by BR′3 to PhHCR-NMe-BR′2 and R′0-BR2. Similar reduction products are isolated from liquid-phase thermolysis of PhHCEt-NMe-OBEt2 (16), whereas gas-phase thermolysis of 16 gives PhCH = NMe, (EtBO)3, and C4H10.

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Trimethylsilyl Cation Affinities to Permethylated Monosaccharides and Simple Crown Ethers in the Gas Phase Using ICR Mass Spectrometry. An Interconnection with FAB Ionization Mechanism.

Journal of the Mass Spectrometry Society of Japan ◽

10.5702/massspec.42.225 ◽

1994 ◽

Vol 42 (4) ◽

pp. 225-235 ◽

Cited By ~ 1

Author(s):

Masami SAWADA ◽

Yasuo OKUMURA ◽

Yoshio TAKAI ◽

Shigetoshi TAKAHASHI ◽

Masaaki MISHIMA ◽

...

Keyword(s):

Mass Spectrometry ◽

Gas Phase ◽

Crown Ethers ◽

Ionization Mechanism ◽

Trimethylsilyl Cation

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Binding interaction of the trimethylgermyl cation with acetophenones in the gas phase †

Journal of the Chemical Society Perkin Transactions 2 ◽

10.1039/b009061l ◽

2001 ◽

pp. 798-803 ◽

Cited By ~ 6

Author(s):

Mustanir ◽

Masaaki Mishima

Keyword(s):

Gas Phase ◽

Binding Interaction

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Relative methylmercury cation affinities in the gas phase determined by high pressure mass spectrometry

Canadian Journal of Chemistry ◽

10.1139/v81-266 ◽

1981 ◽

Vol 59 (12) ◽

pp. 1779-1786 ◽

Cited By ~ 12

Author(s):

John A. Stone ◽

Dena E. Splinter

Keyword(s):

High Pressure ◽

Gas Phase ◽

External Rotation ◽

Equilibrium Constants ◽

Partition Functions ◽

Pulsed Electron Beam ◽

Nitrogen Bases ◽

Relative Affinity ◽

The Difference ◽

Soft Acid

A pulsed electron beam, high pressure mass spectrometer has been used to determine equilibrium constants for the exchange of CH3Hg+ between bases; [Formula: see text] A series of aromatic, hydrocarbon bases has been studied at 417 K and several nitrogen bases have been studied at 580 K. There is a good linear correlation between differences in CH3Hg+ affinity (ΔG0) and H+ affinity for bases in each series. The single sulfur base examined ((C3H7)2S) shows anomalously high relative affinity for CH3Hg+ compared with H+ while two oxygen bases (CH3COOCH3 and C6H5NO2) show lesser relative affinity. These results are in qualitative agreement with the hard–soft acid base theory. ΔH0 and ΔS0 values have been obtained from Arrhenius plots. For a pair of aromatic bases (toluene–ethylbenzene) ΔH0 is of the same magnitude as that for H+ and ΔS0 may be calculated using partition functions for translation and external rotation. For toluene/methylacetate the difference in binding energy is much greater for H+ than for CH3Hg+ and a similar calculation of ΔS0 gives a result not consistent with the experimental value.

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