Pressure effect on the rate and equilibrium constants of the Diels-Alder reaction 9-chloroanthracene with tetracyanoethylene

Kiselev, V. D.; Kashaeva, E. A.; Коновалов, А. И.

doi:10.1016/s0040-4020(98)01093-x

Tetrahedron

1999

DOI: 10.1016/s0040-4020(98)01093-x

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Pressure effect on the rate and equilibrium constants of the Diels-Alder reaction 9-chloroanthracene with tetracyanoethylene

V. D. Kiselev

E. A. Kashaeva

А. И. Коновалов

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Cited by 44 publications

(47 citation statements)

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“…I-5 A recent study is devoted to the reversible Diels--Alder reaction between tetracyanoethylene and 9-chloroanthracene. 6 It was found that the reaction volumes determined by indirect methods (from the difference between the activation volumes of the forward and reverse processes and from the pressure dependence of the equilibrium constant) and by the direct method (from the difference between the partial molar volumes of the adduct and the reagents) are equal within the accuracy of determination. For polar and ionic processes, the contribution of the solvent electrostriction effect to the overall activation volume can be commensurable with and even exceed in magnitude the structural contribution.…”

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Dramatic solvent effect on the volume of the Diels-Alder reaction between tetracyanoethylene and cyclopentadiene

et al. 2000

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The partial molar volumes (V) and the enthalpies of dissolution (Adis/'~ for tetracyanoethylene, cyclopentadiene, and their Diels--Atder adduct were determined at 25 ~ Eleven solvents of the ~-and n-donor type were used. The use of alkylbenzenes as solvents t'or tetracyanoethylene induces pronounced changes in the enthalpy of dissolution (up to 26 kJ tool -l) and in the partial molar volume (up to I I cm 3 tool-I), whereas these parameters for the adduct change slightly. The V and ,5,jisH values for cyclopentadiene virtually do not depend on the nature of the solvent. In the case of tetracyanoethylene and the adduct in n-donor solvents, considerable variations of the Vand AdisH values are observed; they are not linear functions of the change in the partial molar volume of the adduct. Theretbre, the reaction volumes in acetonitrile (-40.69) and ethyl acetate (-45.56) differ sharply from those in o-xylene (-24.28) and mesitylene (-21.76 cm 3 mot-I).Key words: partial molar volume, reaction volume, tetrzcyanoethyIene, specific interactions, Oiels--Alder reaction.The use of elevated pressures provides data on the activation and reaction volumes of chemical reactions and allows more precise elucidation of the nature of the activated complex and its location on the reaction coordinate. I-5 A recent study is devoted to the reversible Diels--Alder reaction between tetracyanoethylene and 9-chloroanthracene. 6 It was found that the reaction volumes determined by indirect methods (from the difference between the activation volumes of the forward and reverse processes and from the pressure dependence of the equilibrium constant) and by the direct method (from the difference between the partial molar volumes of the adduct and the reagents) are equal within the accuracy of determination. For polar and ionic processes, the contribution of the solvent electrostriction effect to the overall activation volume can be commensurable with and even exceed in magnitude the structural contribution. 7 A more accurate estimation of the contribution of solvent electrostriction in the solvation of a polar or ionic activation complex requires consideration of the influence of the variable properties of the medium on the reaction rate at elevated pre~ure, a An influence of the solvent on the activation volume has been established for many processes accompanied by the formation of polar or ionic states. I-9 Testing of the process using the data on the influence of lithium perchlorate in diethyl ether on the cycloaddition rate showed that the activation complex in the Diels--Alder reaction involving tetracyanoethylene should be relatively nonpolar. 1~ This means that solvent electrostriction in the solvation shell of the activated complex should be insignificant, in this work, we studied the reaction of tetracyanoethylene with cyclopentadiene in different solvents of the rt-and n-donor type (Scheme I). Tetracyanoethylene is a strong n-acceptor (electron affinity 2.88 eVil); however, its rc-acceptor properties should not be manifested in full mea...

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Dramatic solvent effect on the volume of the Diels-Alder reaction between tetracyanoethylene and cyclopentadiene

et al. 2000

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“…One of the most intensively studied is the effect of pressure on the rate and equilibrium of the DielsAlder reaction (DAR) [3][4][5][6][7][8].…”

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“…2) of forward and retro reactions. This allows calculation of the volumes of reaction V r-n and activation ( V = forw , V = ret ) and allows comparing them with the value of the reaction volume calculated independently from the difference in the partial molar volumes (PMV) of the adduct and reagents [8]:…”

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“…3 confirm the validity of Eqs. 1 and 2 [8]. In some cases acceleration of the retro-DAR at elevated pressure is of particular interest.…”

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“…V = forw / V r-n > 1, was observed [5][6][7]. There are only a few direct measurements of the pressure influence on the rate of adduct decomposition [8,[15][16][17]. Why the AC in isopolar DAR should be more compact than the cycloadduct is not yet understood [15][16][17][18][19][20].…”

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Anomalies in the Change of Volumetric Parameters of the Diels–Alder Reaction in Solution

et al. 2012

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In this article negative values of the activation volume in retro-Diels-Alder reactions are interpreted in terms of the different possibilities of penetration of the solvent molecules into the sterically branched structures of the adduct and activated complex. Empty spaces, inaccessible to penetration of solvent molecules, lead to increases of the molar volume of the screened adducts in solution and, consequently, to a less negative value of the Diels-Alder reaction volume. The values of partial molar volumes of anthracene, maleic anhydride and the adducts cyclopentadiene-maleic anhydride, anthracene-maleic anhydride and anthracene-tetracyanoethylene, in several solvents, were calculated from the solution density data.

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Why can the activation volume of the cycloadduct decomposition in isopolar retro‐Diels–Alder reactions be negative?

Kiselev

2009

Int J of Chemical Kinetics

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Rate constants of the Diels-Alder cycloaddition reaction of anthracene with tetracyanoethylene, enthalpy of solution of reactants and adduct, enthalpy of the reaction in solution, enthalpy and entropy of activation of the forward and retro-Diels-Alder reactions were determined in 14 solvents. Temperature and pressure effects on the rate of the decomposition of the adduct formed from 9-chloroanthracene and tetracyanoethylene were studied. Since the electrostriction effect can be excluded from the consideration of the isopolar Diels-Alder reaction, negative values of the activation volume in the retro-Diels-Alder reactions can be caused by the different possibilities of penetration of the solvent molecules to large steric branched structures of the transition states and adducts.

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Pressure effect on the rate and equilibrium constants of the Diels-Alder reaction 9-chloroanthracene with tetracyanoethylene

Cited by 44 publications

References 19 publications

Dramatic solvent effect on the volume of the Diels-Alder reaction between tetracyanoethylene and cyclopentadiene

Dramatic solvent effect on the volume of the Diels-Alder reaction between tetracyanoethylene and cyclopentadiene

Anomalies in the Change of Volumetric Parameters of the Diels–Alder Reaction in Solution

Why can the activation volume of the cycloadduct decomposition in isopolar retro‐Diels–Alder reactions be negative?

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