Planar Tetracoordinate Carbon in Organoboron Compounds: ab initio Computational Study

Gribanova, T. N.; Minyaev, R. M.; Минкин, В. И.

doi:10.1135/cccc19991780

Cited by 31 publications

(31 citation statements)

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“…Some building blocks in Scheme 5h ave also been employed to build ptC compounds.F or example,u sing C 5 2À , the smallest carbon cluster containing ap tC as the starting point, Vela and co-workers [42] designed as eries of ptC compounds 15 a-c ( Figure 15). Minkin and co-workers [43] found new building blocks similar to those in Scheme 5a nd constructed 15 d and 15 e.F our cyclic hydrocarbons containing ap tC,i ncluding 13 i-l,w ere proposed by Merino and coworkers. [44] More isoelectronic analogues of the structures in Schemes 4a nd 5w ere designed by Sastry and co-workers.…”

Section: Angewandte Chemiementioning

confidence: 81%

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Four Decades of the Chemistry of Planar Hypercoordinate Compounds

et al. 2015

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The idea of planar tetracoordinate carbon (ptC) was considered implausible for a hundred years after 1874. Examples of ptC were then predicted computationally and realized experimentally. Both electronic and mechanical (e.g., small rings and cages) effects stabilize these unusual bonding arrangements. Concepts based on the bonding motifs of planar methane and the planar methane dication can be extended to give planar hypercoordinate structures of other chemical elements. Numerous planar configurations of various central atoms (main-group and transition-metal elements) with coordination numbers up to ten are discussed herein. The evolution of such planar configurations from small molecules to clusters, to nanospecies and to bulk solids is delineated. Some experimentally fabricated planar materials have been shown to possess unusual electrical and magnetic properties. A fundamental understanding of planar hypercoordinate chemistry and its potential will help guide its future development.

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Section: Angewandte Chemiementioning

confidence: 81%

“…Minkin and co-workers [43] found new building blocks similar to those in Scheme 5a nd constructed 15 d and 15 e.F our cyclic hydrocarbons containing ap tC,i ncluding 13 i-l,w ere proposed by Merino and coworkers. [44] More isoelectronic analogues of the structures in Schemes 4a nd 5w ere designed by Sastry and co-workers.…”

Section: +mentioning

confidence: 86%

Four Decades of the Chemistry of Planar Hypercoordinate Compounds

et al. 2015

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“…The strategy suggested by Hoffmann et al to stabilize a ptC entity electronically was based on the replacement of the hydrogens by ligands that are (1) -donors (to assist electron transfer to the electron deficient carbon), and (2) -acceptors (to delocalize the p or -type lone pair), or by incorporating the lone pair into a (4n þ 2) delocalized system. 11 Using Hoffmann's strategy (also called the electronic approach), several ptC molecules have been proposed in silico 14,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] and/or experimentally detected. [38][39][40][41][42][43][44][45][46][47][48] A few realized compounds of nonclassical structures containing ptCs are shown in Figure 2.…”

Section: How To Stabilize a Planar Tetracoordinate Carbon?mentioning

confidence: 99%

“…Using Hoffmann's strategy (also called the electronic approach), several ptC molecules have been proposed in silico 14,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] and/or experimentally detected. [38][39][40][41][42][43][44][45][46][47][48] A few realized compounds of nonclassical structures containing ptCs are shown in Figure 2.…”

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confidence: 99%

Recent advances in planar tetracoordinate carbon chemistry

et al. 2006

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We summarize our contributions on the quest of new planar tetracoordinate carbon entities (new carbon molecules with exotic chemical structures and strange bonding schemes). We give special emphasis on the rationalization why in this type of molecules the planar configuration is favored over the tetrahedral one. We will concentrate on the latter and will show that molecules containing planar tetracoordinate carbons have a stabilizing system of delocalized electrons, which shows similar properties as systems in aromatic molecules.

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“…The bonds formed by the central boron atom with the surrounding boron ligands in system VII are somewhat shorter (1.638 A) than usual single BB bonds. According to the molecular-orbital analysis, system VII, as well as the previously studied stable systems with planar four-coordinate carbon and nitrogen atoms [4,5,7], is characterized by a stable p system with two occupied bonding p orbitals and unoccupied antibonding p orbitals (Fig. 2).…”

Section: äääääääääääämentioning

confidence: 99%

Stabilization of Planar Four-Coordinate Boron, Carbon, and Silicon Atoms in Borane Clusters: A Quantum-Chemical Study

Gribanova

Minyaev

2005

Russ J Gen Chem

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Stability of a series of neutral and charged borane clusters containing planar four-coordinate boron centres was predicted by the density functional theory DFT (B3LYP/6-311+G**). The possibility of the modification of these systems to obtain new stable compounds with planar four-coordinate carbon and silicon atoms was examined. The calculations show that the substituted systems should be more stable than the isoelectronic boron analogs.The possibilities of the stabilization of planar hypercoordinated centers of main-group elements are actively studied today [1]. The strategy of the stabilization of the planar four-coordinate carbon center [2] suggested by Hoffmann et al. not only made it possible to find numerous compounds with a planar carbon atom [1, 335], but also was successfully used for stabilizing neutral and charged derivatives of the planar four-coordinate nitrogen atom [6,7]. Unlike the case of carbon and nitrogen atoms, when the decisive factor in stabilization of the planar conformation consists in the delocalization of excessive electron density of the four-coordinate center by introduc-ÄÄÄÄÄÄÄÄÄÄÄÄ ing electropositive p-acceptor ligands, the stabilization of compounds of the d-lumomer type with four-coordinate boron can be achieved by introducing p-donor and s-acceptor substituents [8]. At the same time, available calculations suggest the possibility of stabilization of planar hypercoordinated boron centers in boron surroundings. Examples of such systems are planar systems I and II with four-coordinate boron centers [9, 10], planar systems III and IV with sixcoordinate boron centers [11,12], and also clusters V and VI and other compounds including hypercoordinated boron centers with a flattened configuration of bonds [13315].

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Planar Tetracoordinate Carbon in Organoboron Compounds: ab initio Computational Study

Cited by 31 publications

References 0 publications

Four Decades of the Chemistry of Planar Hypercoordinate Compounds

Four Decades of the Chemistry of Planar Hypercoordinate Compounds

Recent advances in planar tetracoordinate carbon chemistry

Stabilization of Planar Four-Coordinate Boron, Carbon, and Silicon Atoms in Borane Clusters: A Quantum-Chemical Study

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