A. Yu. Bykov

A new method of synthesis of the B3H8− anion

A new method of synthesis of the B3H8− anion has been suggested. The method uses the reaction of some metal halides (CuCl, SnCl2, CrCl3, PbF2, PbCl2, PbBr2, and BiCl3) with sodium tetrahydroborate. It is characterized by high (up to quantitative) yields and simplicity of isolation of the target products ((n-C4H9)4N)[B3H8] and Cs[B3H8].

The chemistry of the octahydrotriborate anion [B3H8]−

The review integrates data on the structure, methods of synthesis, reactivity, and coordination properties of the octahydrotriborate anion.

Reactions of sodium tetrahydroborate with alkyl and aryl halides: A new approach to the synthesis of B3H8− and B12H122− anions

A new method for the synthesis of the B3H8− anion based on the reactions of alkyl and aryl halides (C2H4Cl2, C6H5CH2Cl, C4H9Br, (C6H5)3CCl, C10H7CH2Cl, CH2I2, C2HCl3) with sodium tetrahydroborate in diglyme was proposed. The method is characterized by high (up to quantitative) yields and easy isolation of the target products, (n-C4H9)4N)[B3H8] and Cs[B3H8], and also easy preparation of a salt of higher hydroborate anion, B12H122−, without multistage purification from impurities of other anions of this series.

Hydrolysis of nitrilium derivatives of the closo-decaborate anion [2-B10H9(N≡CR)]– (R = CH3, C2H5, C(CH3)3, or C6H5)

Reaction of tetrabutylammonium salts of [2-B10H9(N≡CR)]– (R = CH3, C2H5, C(CH3)3, or C6H5) anions with water results in N-borylated iminols (Bu4N)[2-B10H9NH=C(OH)R], and in the presence of an alkali, corresponding N-substituted amides (Bu4N)2[2-B10H9NH-C(=O)R] are formed. The compounds obtained are identified by IR, ESI/MS, and 1H, 11B, and 13C NMR spectroscopy. The crystal structure of compound (Bu4N)[2-B10H9(Z-{NHC(OH)C2H5})] is studied by X-ray diffraction.

A new method for the synthesis of carboxonium derivatives of the closo-decaborate anion [2,6-B10H8(O2CR)]–, where R = CH3, C2H5

A single-stage scheme for the synthesis of carboxonium derivatives of the closo-decaborate anion by the reaction between the [B10H11]– anion and carboxylic acids was proposed. Target compounds were separated and characterized by IR and 1H, 11B, 13C NMR spectroscopy. In addition to the target compounds, closo-decaborate cluster opening products ere formed, and in the reaction between the closo-decaborate anion and acetic acid, a polymeric product was observed. The polymeric product (Ph4P)n[2,6,3,7-B10H6O2CCH3]n was characterized by X-ray diffraction.

Modern aspects of the chemistry of complex boron and aluminum hydrides

The review deals with new methods of synthesis of complex tetrahydroborates and tetrahydroaluminates and their coordination compounds, initial reagents for synthesis of borides, catalyst precursors, and materials for hydrogen economy.

Synthesis of Boron-Containing Siloxanes by Reaction of Hydroxy-closo-Decaborates with Dihalosilanes

A new approach to the preparation of boron-containing siloxanes based on cluster boron anions has been suggested. This approach consists in the reaction of hydroxy derivatives of closo-decaborate anion [B10H10–n(OH)n]2– (n = 1, 2) with dihalosilanes SiR2Cl2 (R = CH3, t-C4H9, C6H5). The obtained compounds have been characterized by IR, ESI/MS, and NMR (1H, 11B, 13C) spectroscopy.

Structure, physicochemical properties, and reactivity of the [B9H9]2– anion

Data on the structure, properties, and reactivity of one of the least studied 3D aromatic clusters—nonahydro-closo-nonaborate anion [B9H9]2–—have been systematized. It has been shown that the key aspects of its reactivity are related to structural flexibility, which essentially distinguishes the [B9H9]2– anion from the higher representatives of closo-borate anions.

Nickel(II) and Iron(II) coordination compounds with octahydrotriborate(1–) anion [ML3]{B3H8}2 (M = Fe2+, Ni2+; L = bipy, phen)

Methods of synthesis have been developed for new types of promising precursors of metal borides, coordination compounds [ML3]B{3H8{2 (M = Fe2+, Ni2+; L = bipy, phen), using modified procedures of synthesis of octahydrotriborate anion. Compounds [Ni(bipy)3]B{3H8}2, [Ni (phen)3]B{3H8}2 and [Fe(phen)3]B{3H8}2 were prepared and characterized by single-crystal X-ray diffraction.

A new method of synthesis of the B3H 8 − anion

A new method of synthesis of the B3H8− anion has been suggested. The method uses the reaction of some metal halides (CuCl, SnCl2, CrCl3, PbF2, PbCl2, PbBr2, and BiCl3) with sodium tetrahydroborate. It is characterized by high (up to quantitative) yields and simplicity of isolation of the target products ((n-C4H9)4N)[B3H8] and Cs[B3H8].