Syntheses, Structures, and Reactivities of N-Heterocyclic Carbene-Coordinated Aminoborane Complexes.

Recent research has attracted considerable attention toward N-heterocyclic carbene-coordinated boranes (NHC-borane) and their B-substituted derivatives because of their unique characteristics. In the present work, we focused on the syntheses, structures, and reactivities of such types of amine complexes, [NHC·BH2NH3]X ((NHC = IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and IMe (1,3-dimethylimidazol-2-ylidene); X = Cl, I, OTf). We have developed a synthetic method to access NHC·BH2NH2 through the reaction of NaH with [IPr·BH2NH3]I, which was synthesized by the reaction of IPr·BH2I with NH3. As a Lewis base, NHC·BH2NH2 could further react with HCl or HOTf to produce the corresponding salts of [IPr·BH2NH3]+. IPr·BH2NH2BH2X (X = Cl, I) were synthesized by the reaction of HCl/I2 with IPr·BH2NH2BH3 and then converted to [IPr·BH2NH2BH2·IPr]X (X = Cl, I) by reacting with IPr. The IMe-coordinated boranes reacted quite similarly. The preliminary results revealed that the introduction of the NHC molecule has a considerable impact on the solubility and reactivities of aminoboranes.

Facile Synthetic Method of Na[BH3(NH2BH2)2H] Based on the Reactions of Sodium Amidoborane (NaNH2BH3) with NiBr2 or CoCl2.

The reactions of sodium amidoborane (NaNH2BH3) with NiBr2 have been investigated, and the results showed that black precipitate 1 including the NiBNHx composites could be obtained. From the aqueous solution of the precipitate 1, the hydrolysis product Ni-B (2) was isolated and characterized. Both the in situ formed precipitate 1 and the hydrolysis product 2 can catalyze the formation of Na[BH3(NH2BH2)2H]. CoCl2 showed comparable performance with NiBr2. Based on these results, a facile method for the synthesis of Na[BH3(NH2BH2)2H] has been developed. This work provides insights into studying experimental methods for the synthesis of long B/N chain complexes and developing boron and nitrogen chemistry.

Hydroboration Reaction and Mechanism of Carboxylic Acids using NaNH2(BH3)2, a Hydroboration Reagent with Reducing Capability between NaBH4 and LiAlH4.

Hydroboration reactions of carboxylic acids using sodium aminodiboranate (NaNH2[BH3]2, NaADBH) to form primary alcohols were systematically investigated, and the reduction mechanism was elucidated experimentally and computationally. The transfer of hydride ions from B atoms to C atoms, the key step in the mechanism, was theoretically illustrated and supported by experimental results. The intermediates of NH2B2H5, PhCH═CHCOOBH2NH2BH3-, PhCH═CHCH2OBO, and the byproducts of BH4-, NH2BH2, and NH2BH3- were identified and characterized by 11B and 1H NMR. The reducing capacity of NaADBH was found between that of NaBH4 and LiAlH4. We have thus found that NaADBH is a promising reducing agent for hydroboration because of its stability and easy handling. These reactions exhibit excellent yields and good selectivity, therefore providing alternative synthetic approaches for the conversion of carboxylic acids to primary alcohols with a wide range of functional group tolerance.

A general method for the synthesis of covalent and ionic amine borane complexes containing trinitromethyl fragments.

A general approach for the synthesis of covalent and ionic amine borane complexes containing trinitromethyl fragments has been developed through metathesis reactions between amine chloroborane complexes and potassium salt of trinitromethyl (K[C(NO2)3]). Five covalent and ionic trinitromethyl amine borane complexes have been synthesized in good yields with high purity and it is found that the ionic complex, [H2B(NH3)2][C(NO2)3], might be a promising energetic material on the basis of the investigation of its thermal decomposition behaviour.