The new approach to formation of exo boron–oxygen bonds from the decahydro-closo-decaborate(2-) anion

Klyukin, I. N.; Кубасов, А. С.; Limarev, Ilya P.; Жданов, А. П.; Matveev, E. Yu.; Polyakova, I. N.; Zhizhin, K. Yu.; Кузнецов, Н. Т.

doi:10.1016/j.poly.2015.09.025

Cited by 34 publications

(5 citation statements)

References 36 publications

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“…product as a result of the EINS process, initiated by hydrogen halides [26], sulfuric [57] or carbonic acids [23,24,58]. Second nucleophilic substitution also occurs in the equatorial position of closoborane in trans position to the X − substituent with the formation of the 2,8-[B 10 H 8 X 2 ] 2− product (or its optical isomer 2,7-[B 10 H 9 X 2 ] 2− ) [23,25,26,[57][58][59][60]. In…”

Section: Resultsmentioning

confidence: 99%

The Mechanism of Halogenation of Decahydro-closo-Decaborate Dianion by Hydrogen Chloride

Golub

Filippov

Belkova

et al. 2021

Russ. J. Inorg. Chem.

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The mechanism of the halogenation of decahydro-closo-decaborate dianion [B 10 H 10 ] 2− by HCl via the electrophile-induced nucleophilic substitution (EINS) was explored at M06/6-311++G(d,p) level of DFT theory in acetonitrile (MeCN) taking into account non-specific solvent effect (SMD model). The dihydrogen-bonded (DHB) complexes are the first and important reaction intermediates of the EINS process since they determine the principal direction of HCl attack and lead to the proton transfer to the most reactive and elongated B-H bond. Upon the successive replacement of H − with Cl − in the closo-borane structure, a gradual increase in the electron deficiency of closo-borane and the electrophilicity of boron atoms are observed. The lack of stabilization of the η 2 -H 2 complexes for the subsequent stages of the reaction is associated with an increased electrophilicity of boron atoms in substituted closo-boranes. An increased electrophilicity of boron atoms in substituted closo-boranes and higher activation energy of each subsequent stage during the EINS process hamper the reaction and completely stop the chlorination on 3rd or 4th reactions steps. Thus, the data obtained indicate that for the selective synthesis of halogenated products [B 10 H (10 -x) Cl x ] 2− (x = 5-7) it is necessary to use an approach alternative to the simple acid-initiated nucleophilic substitution. This could be the activation of the bond by Lewis superacids or transition metal catalysis.

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Section: Resultsmentioning

confidence: 99%

The Mechanism of Halogenation of Decahydro-closo-Decaborate Dianion by Hydrogen Chloride

Golub

Filippov

Belkova

et al. 2021

Russ. J. Inorg. Chem.

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“…[13][14][15][16][17][18] Previously we discovered convenient method of synthesis of disubstituted oxonium derivatives using CF 3 SO 3 H as electrophilic inductor. [19] This method is quite universal and allows to produce disubstituted derivatives containing various exo-polyhedral bonds. In our case we tried to obtain closo-decaborate derivatives with two nitrilium groups.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of New Bioinorganic Systems Based on Nitrilium Derivatives of closo-Decaborate Anion and meso-Arylporphyrins with Pendant Amino Groups

Ezhov¹,

Vyal’ba²,

Kluykin³

et al. 2017

MHC

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“…Previously, several disubstituted derivatives of closo-borate anions have been investigated. Disubstituted oxonium and nitrilium derivative were obtained on the basis of interactions between closo-decaborate anions [B 10 H 10 ] 2− and ethers or nitriles, in the presence of trifluoromethanic acid CF 3 SO 3 H as an electrophile inducer [31,32].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

et al. 2023

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A theoretical modelling of the interaction process between a protonated complex of carboxonium derivative [2,6-B10H8O2CCH3*Hfac]0 and acetonitrile molecule CH3CN was carried out. As a result of the process, a trisubstituted [B10H7O2CCH3(NCCH3)]0 derivative was formed. This reaction has an electrophile-induced nucleophilic substitution (EINS) mechanism. The main intermediates and transition states of the substitution process were established. As in the case of all previously investigated EINS processes, the key intermediate was an anion with a dihydrogen H2 fragment attached to one boron atom (B(H2) structure motif). The process of nucleophilic substitution can proceed on a different position of the cluster cage. The main potential pathways were assessed. It was established that substitution on the B4 position of the cluster cage was the most energetically favourable, and the [2,4,6-B10H7O2CCH3(NCCH3)]0 isomer was formed.

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The new approach to formation of exo boron–oxygen bonds from the decahydro-closo-decaborate(2-) anion

Cited by 34 publications

References 36 publications

The Mechanism of Halogenation of Decahydro-closo-Decaborate Dianion by Hydrogen Chloride

The Mechanism of Halogenation of Decahydro-closo-Decaborate Dianion by Hydrogen Chloride

Synthesis of New Bioinorganic Systems Based on Nitrilium Derivatives of closo-Decaborate Anion and meso-Arylporphyrins with Pendant Amino Groups

Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

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