Acid-Induced Opening of [closo-B10H10]2–as a New Route to 6-Substitutednido-B10H13Decaboranes and Related Carboranes

Бондарев, Олег Иванович; Sevryugina, Yulia; Jalisatgi, Satish S.; Hawthorne, M. Frederick

doi:10.1021/ic3014267

Cited by 39 publications

(46 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…strength of a proton donor, for example, the use of superacids, will not, as expected, decrease in the reaction barrier of H 2 elimination, but as well as in the case of [B 6 H 6 ] 2− [38,[72][73][74] cause its double protonation and results in the formation of neutral of B 10 H 12 [75], which is an intermediate of the proton-induced cageopening reaction [22,76]. To determine the optimal pathway -the one characterized by the lowest activation energy, , (Scheme 4, Scheme S1)-we have analyzed the hydride donor abilities (HDA MeCN ) of B-H bond in halogenated [B 10 H (10 -x) Cl x ] 2− (x = 0-9) products in acetonitrile.…”

Section: G °δmentioning

confidence: 68%

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: G °δmentioning

confidence: 68%

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

“…Synthesis of ortho ‐carboranes, 1‐R‐2‐R′‐4‐R′′‐1,2‐C 2 B 10 H 10 , from substituted alkynes and 6‐R′′‐ nido ‐B 10 H 13 , generated by an acid‐induced opening of [ closo ‐B 10 H 10 ] 2– , was reported as shown in Figure . Another carborane species, 1‐phenyl‐4‐mesityl‐1,2‐ closo ‐carborane, was prepared in a yield of 67 % in the presence of a catalytic amount of [BMIM]Cl within three hours, while the reaction in toluene solution with N , N ‐dimethylaniline as a Lewis base afforded the same product after three days in a yield of 38 %.…”

Section: Application Of Ionic Liquids In Synthesismentioning

confidence: 99%

“…Synthesis of ortho ‐carborane derivatives from closo ‐B 10 H 10 2– . Reprinted with permission from ref . Copyright (2012) American Chemical Society.…”

Section: Application Of Ionic Liquids In Synthesismentioning

confidence: 99%

Ionic Liquids: Recent Advances and Applications in Boron Chemistry

Zhu

Hosmane

2017

Eur J Inorg Chem

View full text Add to dashboard Cite

Ionic liquids (ILs) are a type of low‐melting salts, which are generally nonvolatile, have low vapor pressure, very high boiling point, and excellent thermal stability. In addition, they have unique physical and chemical properties including highly variable viscosity, in contrast to common inorganic salts and organic liquids. Consequently, they have found potential applications in the broad area of green chemistry and as electrolytes. Recently, advances have been made in the use of ILs in boron chemistry, and as such various boron‐containing ILs have been reported and their applications in classic organic synthesis have been explored. Interestingly, many boron‐related reactions, such as hydroboration, were explored in ionic liquid media. This microreview mainly focuses on the progress of boron‐containing ILs and reactions involving boron compounds in ILs.

show abstract

“…3). 36 [HCB 11 Cl 11 ]binds via one 15 of its meta-Cl atoms and the corresponding Pd-Cl distance (2.5041(5) Å) is much longer than the Pd-Cl distance in (POCOP)Pd-Cl (2.371(18) Å). 37 Thus, although binding to the chlorine on the carborane cage is possible, even the soft Pd center prefers to bind the B-OTf oxygen in [HCB 11 Cl 10 OTf].…”

mentioning

confidence: 99%

“…14 In related polyhedral borane chemistry, syntheses of nido-6-OTf-B 10 H 13 , nido-6-cyclohexyl-B 10 H 13 , nido-5-OTf-B 10 H 13 , and MeNB 11 H 5 Me 5 OTf have been reported. [15][16][17][18] We became interested in exploiting OTf as a desirable substituent on the carborane cage and in investigating the behaviour of the resultant anions as WCAs in silylium-catalyzed hydrodefluorination [19][20][21][22] and toward highly unsaturated transition metal cations. 23 We surmised that a B-OTf moiety would still be weakly coordinating and may bring advantages of 19 F NMR spectroscopy and altered solubility.…”

mentioning

confidence: 99%