New Synthesis Method of N-Monosubstituted Ammonium-closo-Decaborates

Жданов, А. П.; Воинова, В. В.; Klyukin, I. N.; Кубасов, А. С.; Zhizhin, K. Yu.; Кузнецов, Н. Т.

doi:10.1007/s10876-019-01628-2

Cited by 16 publications

(7 citation statements)

References 54 publications

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“…This complex is a key intermediate of the process which determines the selectivity of nucleophilic substitution, since stabilization of H 2 at one of the vertices of the closo -borane octahedron determines the position of nucleophilic substitution at this vertex. Notably, this complex was not revealed at the gas phase calculations of Cl − [ fac HB 6 H 6 ] − [ 68 ]. Similarly to the Cl − [(η 2 -H 2 )B 10 H 9 ] − [ 49 ] it could be stabilized only in the presence of HX acid residue X − .…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2021

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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).

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Section: Resultsmentioning

confidence: 99%

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

et al. 2021

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“…The substituents in compounds 7 and 8 are rotated in such a way that they form short NH•••HB contacts of ~2.23-2.24 Å length with the B(8 )H group of the opposite unsubstituted dicarbollide ligand, whereas in the structure of 9 the short NH•••HB contact of 1.76 Å is formed with the B(4 )H group of the opposite dicarbollide ligand. These distances are less than the sum of the van der Waals radii of two hydrogen atoms (2.4 Å), which is indicative of the weak N-H δ+ •••H δ--B dihydrogen bonding that is commonly observed in compounds containing boron and nitrogen atoms [90][91][92][93][94][95][96][97][98][99][100][101]. It was shown that in the case of the imidate derivative of cobalt bis(dicarbollide…”

Section: Discussionmentioning

confidence: 99%

Synthesis of Boronated Amidines by Addition of Amines to Nitrilium Derivative of Cobalt Bis(Dicarbollide)

et al. 2021

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A series of novel cobalt bis(dicarbollide) based amidines were synthesized by the nucleophilic addition of primary and secondary amines to highly activated B-N+≡C–R triple bond of the propionitrilium derivative [8-EtC≡N-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]. The reactions with primary amines result in the formation of mixtures of E and Z isomers of amidines, whereas the reactions with secondary amines lead selectively to the E-isomers. The crystal molecular structures of E-[8-EtC(NMe2)=HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)], E-[8-EtC(NEt2)=HN-3,3′-Co(1,2- C2B9H10)(1′,2′-C2B9H11)] and E-[8-EtC(NC5H10)=HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] were determined by single crystal X-ray diffraction.

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“…(Diacetoxyiodo)benzene PhI(OAc) 2 was used without additional purification. Nitrilium derivatives 1a – g were synthesized by described methods [ 58 ].…”

Section: Methodsmentioning

confidence: 99%

Fused 1,2-Diboraoxazoles Based on closo-Decaborate Anion–Novel Members of Diboroheterocycle Class

et al. 2021

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The novel members of the 1,2-diboraoxazoles family have been obtained. In the present work, we have carried out the intramolecular ring-closure reaction of borylated iminols of general type [B10H9N=C(OH)R]− (R = Me, Et, nPr, iPr, tBu, Ph, 4-Cl-Ph). This process is conducted in mild conditions with 83–87% yields. The solid-state structures of two salts of 1,2-diboraoxazoles were additionally investigated by X-ray crystallography. In addition, the phenomena of bonding interactions in the 1,2-diboraoxazole cycles have been theoretically studied by the Quantum Theory of Atoms in Molecules analysis. Several local and integral topological properties of the electron density involved in these interactions have been computed.

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New Synthesis Method of N-Monosubstituted Ammonium-closo-Decaborates

Cited by 16 publications

References 54 publications

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

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

Synthesis of Boronated Amidines by Addition of Amines to Nitrilium Derivative of Cobalt Bis(Dicarbollide)

Fused 1,2-Diboraoxazoles Based on closo-Decaborate Anion–Novel Members of Diboroheterocycle Class

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