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--- en:reactivity:radical_addition:objects [2026/09/16 15:18] – created abc
+++ en:reactivity:radical_addition:objects [2026/09/23 09:23] (current) – abc
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 ====== Objects of Investigation: Basic Set of Reactions ======
-To make a background of discussions of reactivity, the following set of reagents was chosen: radicals //CH<sub>3</sub><sup>•</sup>//, //CH<sub>3</sub>O<sup>•</sup>//, //CCl<sub>3</sub><sup>•</sup>//, //CF<sub>3</sub><sup>•</sup>//, and //HOO<sup>•</sup>// and vinyl monomers //CH<sub>2</sub>CHX//: \\
+To make a background of discussions of reactivity, the following set of reagents was chosen: radicals //CH<sub>3</sub><sup>•</sup>//, //CH<sub>3</sub>O<sup>•</sup>//, //CCl<sub>3</sub><sup>•</sup>//, //CF<sub>3</sub><sup>•</sup>//, and //HOO<sup>•</sup>// and vinyl monomers //CH<sub>2</sub>CHX//:
-ethene (//Eth//, //CH<sub>2</sub>CH<sub>2</sub>//), propene (//Prop//, //CH<sub>2</sub>CH-CH<sub>3</sub>//), styrene (//St//, //CH<sub>2</sub>CH-C<sub>6</sub>H<sub>5</sub>//), vinylacetate (//VA//, //CH<sub>2</sub>CH-OCOCH<sub>3</sub>//), methylacrylate (//MA//, //CH<sub>2</sub>CH-COOCH<sub>3</sub>//), acrylic nitryl (//AN//, //CH<sub>2</sub>CH-CN//), vinylchloride (//VCl//, //CH<sub>2</sub>CHCl//), and vinylidenchloride (//VCl2//, CH<sub>2</sub>CCl<sub>2</sub>). For these monomers, both positions of attack were considered. In addition, reactivity of monomers with conjugated bonds toward //CH<sub>3</sub><sup>•</sup>// and //HOO<sup>•</sup>// were considered((butadiene (//Bu2ene//), hexatriene (//Hex3ene//), vinylnaphthalene (//ViNaph//), 2- and 4-vinylpyridines (//ViPy//), and 2- and 4-vinylpyrimidines (//ViPm//) )). The total number of calculated TSs was somewhere around 100.
+ethene (//Eth//, //CH<sub>2</sub>CH<sub>2</sub>//), propene (//Prop//, //CH<sub>2</sub>CH-CH<sub>3</sub>//), styrene (//St//, //CH<sub>2</sub>CH-C<sub>6</sub>H<sub>5</sub>//), vinylacetate (//VA//, //CH<sub>2</sub>CH-OCOCH<sub>3</sub>//), methylacrylate (//MA//, //CH<sub>2</sub>CH-COOCH<sub>3</sub>//), acrylic nitryl (//AN//, //CH<sub>2</sub>CH-CN//), vinylchloride (//VCl//, //CH<sub>2</sub>CHCl//), and vinylidenchloride (//VCl2//, CH<sub>2</sub>CCl<sub>2</sub>). For these monomers, both positions of attack were considered. In addition, reactivity of monomers with conjugated bonds toward //CH<sub>3</sub><sup>•</sup>// and //HOO<sup>•</sup>// were considered((butadiene (//Bu2ene//), hexatriene (//Hex3ene//), vinylnaphthalene (//ViNaph//), 2- and 4-vinylpyridines (//ViPy//), and 2- and 4-vinylpyrimidines (//ViPm//) )). The total number of calculated Transition States was somewhere around 100.
-All TSs had the same topology as shown [[.:ts|above]]. Among the possible conformations of products, those ones were chosen in which the new substituent (formerly the radical) was perpendicular to the original plane of the monomer. Table I presents the main geometric characteristics of TSs of β-attack (attack on the unsubstituted position of the //C=C// bond). One may judge from the table that TS geometries within a series remain practically constant. Comparison of r<sup>prod</sup>/r<sup>≠</sup> values shows that the //CH<sub>3</sub><sup>•</sup>// addition reaction has the earliest TS and the //HOO<sup>•</sup>// addition the latest, in due agreement with experimental facts.
+All TSs had the same topology as shown [[.:ts|above]]. Among the possible conformations of products, those ones were chosen in which the new substituent (formerly the radical) was perpendicular to the original plane of the monomer. Table I presents the main geometric characteristics of TS of β-attack (attack on the unsubstituted position of the //C=C// bond). One may judge from the table that TS geometries within a series remain practically constant. Comparison of r<sup>prod</sup>/r<sup>≠</sup> values shows that the //CH<sub>3</sub><sup>•</sup>// addition reaction has the earliest TS and the //HOO<sup>•</sup>// addition the latest, in due agreement with experimental facts.
 ** Таблица I. Geometries of TSs of β-addition of radicals to the main set of monomers. **
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 ^ Parameter ^  //HOO<sup>•</sup>//  ^  //CH<sub>3</sub><sup>•</sup>//  ^  //CH<sub>3</sub>O<sup>•</sup>//  ^  //CCl<sub>3</sub><sup>•</sup>//  ^  //CF<sub>3</sub><sup>•</sup>//  ^
 | //r<sup>≠</sup>// (Å) | 1.945 ± 0.01 | 2.24 ± 0.02 | 2.05 ± 0.02 | 2.21 ± 0.01 | 2.22 ± 0.01 |
-| φ  |  101  |  105  |  100  |  107  |  106  |
+| φ (°) |  101  |  105  |  100  |  107  |  106  |
 | θ (°) |  15  |  10  |  11  |  13  |  11  |
 | //R<sub>CC</sub>// (Å) |  1.405 ± 0.01  |  1.385 ± 0.01  |  1.395 ± 0.01  |  1.395 ± 0.01  |  1.395 ± 0.01  |
-| //r<sup>prod</sup>/r<sup>≠</sup>// |  0.735 ±.005  |  0.685 ±.005  |  0.689 ±.001  |  0.702 ±.005  |  0.721 ±.003  |
+| //r<sup>prod</sup>/r<sup>≠</sup>// |  0.735 ±.005  |  0.685 ±.005  |  0.689 ±.001  |  0.702 ±.005  |  0.721 ±.003   |
-| //r<sup>≠</sup>//, distance between reactive centers in TS; //r<sup>prod</sup>// – in product);
+| //r<sup>≠</sup>//, distance between reactive centers in TS; //r<sup>prod</sup>// – in product); φ, angle of attack; θ, torsion of //CH// bonds relative to the horizontal plain. ||||||
-φ, angle of attack; θ, torsion of //CH// bonds relative to the horizontal plain. ||||||
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