Gas-phase stability of tertiary carbenium ions and rates of solvolysis of tertiary derivatives

Müller, Paul; Rossier, Jean-Claude; Abboud, José‐Luis M.

doi:10.1002/1099-1395(200010)13:10<569::aid-poc274>3.0.co;2-h

Cited by 6 publications

References 32 publications

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Ab Initio and Experimental Thermodynamic and Kinetic Study of Proton‐Assisted Bond Activation in Gaseous Hydrocarbons: Deconvolution of Reaction Efficiencies in the Case of Adamantane

Dávalos

Herrero

Quintanilla

et al. 2006

Chemistry A European J

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1) Protonation at all possible sites of adamantane (C(10)H(16)) was studied at the MP2/6-311++G(3df,2p)//MP2/6-311++G(d,p) level. This provided values of the changes in the thermodynamic state functions for these processes. Whenever direct comparison was possible, the agreement with experimental data was very good. 2) By the same means, the reaction paths linking the various species obtained in these reactions were analyzed. 3) Fourier transform ion cyclotron resonance (FT-ICR) spectroscopy was used to determine the rate constants for proton transfer from 16 protonated reference bases to adamantane in the gas phase. Also, the rate constants for the formation of ionic products in these reactions were determined. 4) The experimental reaction rates were successfully predicted and refined on the basis of a simple mechanistic model based on the reaction profiles indicated above. 5) Our results hint at the potential usefulness of this approach for mechanistic studies.

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Ab Initio and Experimental Thermodynamic and Kinetic Study of Proton‐Assisted Bond Activation in Gaseous Hydrocarbons: Deconvolution of Reaction Efficiencies in the Case of Adamantane

Dávalos

Herrero

Quintanilla

et al. 2006

Chemistry A European J

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Modeling intrinsic basicities and acidities

Alcamı́

Mó

Yáñez

2002

J of Physical Organic Chem

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We illustrate the potential of ab initio and density functional theory (DFT) methods to model and gain some understanding of the intrinsic reactivity of molecules. We show how the use of high‐level ab initio or DFT calculations permit to rationalize (a) basicity and acidity trends along a series of homologous compounds, namely thiocarbonyl and selenocarbonyl derivatives, α,β‐unsaturated amines, phosphines and arsines, and α,β‐unsaturated alkanes, silanes, germanes and stannanes, (b) the role of intramolecular hydrogen bonds in intrinsic acidities and basicities, (c) the incidence of induced proton transfer process effects on the intrinsic basicity of compounds stabilized by intramolecular hydrogen bonds, (d) hybridization effects on intrinsic basicities, (e) the role of non‐classical structures in intrinsic basicities and (f) the observation of bond cleavage associated with gas‐phase protonation and the influence of these dissociative proton attachment mechanisms on the intrinsic basicity of the system. Copyright © 2002 John Wiley & Sons, Ltd.

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Physical Organic Chemistry of the Gas Phase. Reactivity Trends for Organic Cations

Uggerud¹

2003

Topics in Current Chemistry

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Gas-phase stability of tertiary carbenium ions and rates of solvolysis of tertiary derivatives

Cited by 6 publications

References 32 publications

Ab Initio and Experimental Thermodynamic and Kinetic Study of Proton‐Assisted Bond Activation in Gaseous Hydrocarbons: Deconvolution of Reaction Efficiencies in the Case of Adamantane

Ab Initio and Experimental Thermodynamic and Kinetic Study of Proton‐Assisted Bond Activation in Gaseous Hydrocarbons: Deconvolution of Reaction Efficiencies in the Case of Adamantane

Modeling intrinsic basicities and acidities

Physical Organic Chemistry of the Gas Phase. Reactivity Trends for Organic Cations

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