Study of the controlled temperature reaction between closo-decahydrodecaborate and alcohols in H2SO4 medium

Laila, Zahra; Abi-Ghaida, Fatima; Anwar, Suzan Al; Yazbeck, Ogaritte; Jahjah, Rabih; Aoun, Riman; Tlais, Sami; Mehdi, Ahmad; Naoufal, Daoud

doi:10.3233/mgc-150173

Cited by 6 publications

(2 citation statements)

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“…Such anisotropy in properties leads to the selective formation of 2-[B 10 H 9 X] 2− (X − = Cl, Br, I, OR, COOR, etc.) 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].…”

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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“…The impedance in the functionalization of the closo -decaborate anion is primarily dictated by the electronic environment of the cage; this can be quite challenging due to the presence of 10 inert B–H bonds in a rather stable and comparable chemical environment; B-H bond substitution can proceed via electrophilic or nucleophilic mechanisms in either apical (boron atoms with a co-ordination number of 4) or equatorial (boron atoms with a co-ordination number of 5) positions to yield mono-, di- and poly-substituted derivatives [ 27 , 30 , 31 , 43 ]. A recent soft approach utilized an auto-catalyzed reaction pathway to functionalize (NH 4 ) 2 [B 10 H 10 ] by exploiting the in situ NH 4 + counter cation during the nucleophilic addition of nitriles to the borate cluster via Electrophilic-Induced Nucleophilic Substitution mechanism [ 44 , 45 ].…”

Section: Introductionmentioning

confidence: 99%

Selective Functionalization of Carbonyl Closo-Decaborate [2-B10H9CO]− with Building Block Properties via Grignard Reagents

Mahfouz,

Abi-Ghaida,

Kotob

et al. 2023

Molecules

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A green, fast and selective approach for the synthesis of mono-substituted closo-decaborate derivatives [2-B10H9COR]2− has been established via a nucleophilic addition reaction between the carbonyl derivative of closo-decaborate [2-B10H9CO]− and the corresponding Grignard reagent RMgX, where R is the ethyl, iso-propyl, pentyl, allyl, vinyl and propynyl groups. This approach is accomplished under mild conditions with 70–80% yields. The significance of these derivative is their ability to constitute building blocks for polymeric integration via the allyl, vinyl and propynyl substituents. All products were characterized by 11B, 1H and 13C NMR, elemental analysis and mass spectrometry.

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Synthesis and characterization of click-decahydrodecaborate derivatives by the copper(I) catalyzed [3+2] azide-alkyne cycloaddition reaction

Anwar

Laila

Ramsubhag

et al. 2018

Journal of Organometallic Chemistry

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Study of the controlled temperature reaction between closo-decahydrodecaborate and alcohols in H2SO4 medium

Cited by 6 publications

References 1 publication

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

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

Selective Functionalization of Carbonyl Closo-Decaborate [2-B10H9CO]− with Building Block Properties via Grignard Reagents

Synthesis and characterization of click-decahydrodecaborate derivatives by the copper(I) catalyzed [3+2] azide-alkyne cycloaddition reaction

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