Reaction of the closo-decaborate anion B10H 10 2− with dichloroethane in the presence of hydrogen halides

Drozdova, V. V.; Zhizhin, K. Yu.; Малинина, Е. А.; Polyakova, I. N.; Кузнецов, Н. Т.

doi:10.1134/s0036023607070042

Cited by 13 publications

(6 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

“…many cases, the reaction stops at the second step, but for some systems such as [B 10 H 10 ] 2− with HX (X = Cl, Br, I) in CH 2 Cl 2 [26] or with ROOH [58] ] − is non-rigid and proton can flux [64] along the polyhedron facets and edges with activation barriers 4-15 kcal/mol in the gas phase [61]. In addition, for [ fac HB 10 H 10 ] − in the gas phase the activation barriers of H 2 elimination from the equatorial and apical boron atoms have been found to be 22.8 kcal/mol and 35.3 kcal/mol, respectively [62].…”

Section: Resultsmentioning

confidence: 99%

“…Still, there are problems in controlling the regioselectivity and, especially, the depth of EINS reaction. For example, chlorination of [B 10 H 10 ] 2− by HCl in dichloroethane leads to the mono-, di-and trichlorosubstituted products [26]. At…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Golub

Filippov

Belkova

et al. 2021

Russ. J. Inorg. Chem.

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

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

Golub

Filippov

Belkova

et al. 2021

Russ. J. Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…The spectral data are consistent with that documented. 8, [16][17][18] Apparently, the carbocation abstracted the hydride ion from the boron framework giving the [B 10 H 9 ] -ion, which reacted immediately with the nucleophilic center of the reagent yielding the substituted derivatives of the [2 B 10 H 9 Nu] -ion (compounds 2-7). In the presence of the two fold excess of trityl chloride, second hydride ion was also removed from the boron atom of the neighboring equatorial belt of the cluster giving neutral compounds [eq B 10 H 8 Nu 2 ] 8-10.…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic substitution in closo-decaborate [B10H10]2− in the presence of carbocations

et al. 2010

Self Cite

View full text Add to dashboard Cite

Nucleophilic substitution at the exo polyhedral boron atoms of closo decaborate [B 10 H 10 ] 2-in the presence of carbocations, which were generated in situ from various halocarbons (triphe nylmethyl chloride, 1 bromoadamantan, n butyl bromide), was studied. The reactions carried out in nucleophilic solvents (cyclic ethers and thioethers, N,N disubstituted amides, and car boxylic acids) and in the presence of halocarbons afforded mono and disubstituted compounds with the exo polyhedral B-O and B-S bonds, which contained a molecule of the solvent as substituent. The structures of the compounds synthesized were confirmed by the IR, mass, and 1 H, 11 B, and 13 C NMR spectra.

show abstract

“…Its interaction with strong acids was investigated only for the first reaction step — and only for CF 3 OH [ 21 ]. From one side, hydrogen halides (such as HCl and HBr) are strong inorganic acids which violently react with BH 4 − and cause halogenation of closo -boranes via the electrophile-induced nucleophilic substitution (EINS) mechanism [ 22 , 23 ]. From the other side, the halogen is the electron-withdrawing group (EWG), which should increase electron deficiency at the boron atom, altering the reactivity of the B–H bond in halogen-substituted derivatives.…”

Section: Introductionmentioning

confidence: 99%

The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-closo-hexaborate Dianion

et al. 2021

View full text Add to dashboard Cite

The mechanism of the consecutive halogenation of the tetrahydroborate anion [BH4]− by hydrogen halides (HX, X = F, Cl, Br) and hexahydro-closo-hexaborate dianion [B6H6]2− by HCl via electrophile-induced nucleophilic substitution (EINS) was established by ab initio DFT calculations [M06/6-311++G(d,p) and wB97XD/6-311++G(d,p)] in acetonitrile (MeCN), taking into account non-specific solvent effects (SMD model). Successive substitution of H− by X− resulted in increased electron deficiency of borohydrides and changes in the character of boron atoms from nucleophilic to highly electrophilic. This, in turn, increased the tendency of the B–H bond to transfer a proton rather than a hydride ion. Thus, the regularities established suggested that it should be possible to carry out halogenation more selectively with the targeted synthesis of halogen derivatives with a low degree of substitution, by stabilization of H2 complex, or by carrying out a nucleophilic substitution of B–H bonds activated by interaction with Lewis acids (BL3).

show abstract

Reaction of the closo-decaborate anion B10H 10 2− with dichloroethane in the presence of hydrogen halides

Cited by 13 publications

References 5 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

Nucleophilic substitution in closo-decaborate [B10H10]2− in the presence of carbocations

The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-closo-hexaborate Dianion

Contact Info

Product

Resources

About