Organic molecules with abnormal geometric parameters

Komarov, Igor V.

doi:10.1070/rc2001v070n12abeh000633

Cited by 51 publications

(34 citation statements)

References 226 publications

(285 reference statements)

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“…The interaction of CO 3 2-anion with Li + , Na + , and K + cations results in two types of metal derivatives similar to 6a and 7a. An increase in the cation size on going from acids to the alkali metal salts leads to formation of more symmetric systems in which each alkali metal cation is coordinated to two oxygen centers simultaneously.…”

Section: Resultsmentioning

confidence: 98%

“…Structure and stability of CO 3 2-and CO 4 4-anions and their protonated derivatives. Structure 4 (D 3h symmetry) of the stable form of carbonate anion, CO 3 2-, corresponds to an energy minimum (λ = 0, λ is the number of negative eigenvalues of the Hesse matrix at a given point) on the potential energy surface (PES).…”

Section: Resultsmentioning

confidence: 99%

“…Structure 4 (D 3h symmetry) of the stable form of carbonate anion, CO 3 2-, corresponds to an energy minimum (λ = 0, λ is the number of negative eigenvalues of the Hesse matrix at a given point) on the potential energy surface (PES). According to both types of calculations, a hypothetical tetrahedral anion CO 4 4-(5) corresponds to an energy minimum on the PES; this is consistent with the results of earlier quantum chemical studies.…”

Section: Resultsmentioning

confidence: 99%

“…It in volves the interaction of alkali metal counterions with carbon oxoanions, namely, a carbonate anion CO 3 2-(4) and a CO 4 4-tetraanion (5) of hypothetical orthocarbo nic acid. 14 Systems 6, 7, and 8 (M = Li, Na, K) studied in this work are formed by the interaction of anions 4 and 5 with two, three, and four metal cations, respectively.…”

mentioning

confidence: 99%

“…In this respect, the best developed field is hypercarbon chemistry for which not only a vari ety of non classical hypercarbon compounds have been found but also efficient methods for the design and stabi lization of such systems were developed. [1][2][3][4][5][6][7][8][9] One of the most convenient and promising approaches to the design of systems with hypercoordinate centers is based on the "induced aromaticity" effect. 10 This meth odology involves the incorporation of counterions (usu ally, lithium cations) into originally unstable anionic non classical systems.…”

mentioning

confidence: 99%

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Stabilization of octacoordinate carbon center in metal-containing derivatives of orthocarbonic acid

Gribanova¹,

Gapurenko²,

Minyaev³

2005

Russ Chem Bull

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The electronic and spatial structures of alkali metal compounds CO 3 M 2 , CO 3 M 3 + , and CO 4 M 4 (M = Li, Na, K) were investigated by the ab initio (MP2(full)/6 311+G**) and density functional (B3LYP/6 311+G**) methods. The calculated energies of formation decrease in the order E Li > E Na > E K for all structural types, being determined by steric and orbital interactions. Stable structures with octacoordinate carbon are formed in the case of CO 4 M 4 salts.Key words: octacoordinate carbon, carbon oxoanions, orthocarbonic acid, alkali metals, quantum chemical calculations.Recently, search for and studies of novel types of non classical valence systems containing hypercoordinate atoms of main group elements have been the subject of increasing interest. 1-9 An important problem in chemis try of hypercoordinate compounds, together with the problems of the maximum possible coordination number of an atom of a certain element and corresponding stereo chemical conditions for stabilization of such systems, 1,2,8 is the design of novel systems with unusual stereochemis try or coordination. In this respect, the best developed field is hypercarbon chemistry for which not only a vari ety of non classical hypercarbon compounds have been found but also efficient methods for the design and stabi lization of such systems were developed. 1-9One of the most convenient and promising approaches to the design of systems with hypercoordinate centers is based on the "induced aromaticity" effect. 10 This meth odology involves the incorporation of counterions (usu ally, lithium cations) into originally unstable anionic non classical systems. 1,10-13 This has been successfully imple mented taking various non classical systems including pla nar (1), 11 pyramidal (2), 11 and sandwich (3) 13 structures with hypercoordinate carbon as examples.Recent studies 2,11,13 showed that the role of the lithium counterions is not reduced to the electrostatic stabiliza tion; they are also involved in the charge transfer pro cesses leading to formation of a closed electron shell of * Dedicated to Academicians A. L. Buchachenko and N. S. Zefirov on the occasions of their 70th birthdays.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%