boron and borazine

Discovered by Stock and Pohland in 1926, borazine is the isoelectronic and isostructural inorganic analogue of benzene, where the C[double bond, length as m-dash]C bonds are substituted by B-N bonds. The strong polarity of such heteroatomic bonds widens the HOMO-LUMO gap of the molecule, imparting strong UV-emitting/absorption and electrical insulating properties. These properties make borazine and its derivatives valuable molecular scaffolds to be inserted as doping units in graphitic-based carbon materials to tailor their optoelectronic characteristics, and specifically their semiconducting properties. By guiding the reader through the most significant examples in the field, in this feature paper we describe the past and recent developments in the organic synthesis and functionalisation of borazine and its derivatives. These boosted the production of a large variety of tailored derivatives, broadening their use in optoelectronics, H2 storage and supramolecular functional architectures, to name a few.

Topics: Boron; Boron Compounds; Carbon; Molecular Structure; Nitrogen

Lewis bases react with borazine and polyborazylene, yielding borane adducts. In the case of NH3 (l), ammonia-borane (AB) is formed and quantified using NMR spectroscopy against an internal standard. Calculations indicate that the formation of B(NH2)3 may provide the driving force of this redistribution. Given the complexity and expense of currently known spent AB regeneration pathways, it is suggested that this redistribution chemistry be used to recover AB and improve regeneration methods.

Topics: Ammonia; Boranes; Boron; Boron Compounds; Hydrogen; Lewis Bases; Magnetic Resonance Spectroscopy; Thermodynamics

The substituted borazines have been computationally investigated as new type of receptors for the recognition of fluoride ion. Fluorine, methyl and phenyl groups have been selected as electron-withdrawing, electron-releasing and aromatic substituents for the study employing DFT (B3LYP/6-311+G**) and ab initio (MP2/6-311+G**) levels of calculations. N-substituted borazines have shown higher fluoride ion affinity than their corresponding B-substituted borazines. In the case of fluorinated borazines, the binding affinity of fluoride is enhanced with the increasing number of substitutions. The F⁻ and Cl⁻ ions, generally, prefer to bind with the boron atom of substituted borazine rings, whereas, Br⁻ ion prefers to bind with NH hydrogens of the borazine receptor units. Phenyl derivatives of borazine also showed analogous behavior with halide anions. The binding affinities of halides with fluorinated and phenyl derivatives of borazine have been found to be much higher than the simple borazine receptor molecule. The NBO analyses performed for the complexation of F⁻ ion with fluorinated borazines suggest that the Lewis energy contribution in the total SCF energy enhanced with increasing the substitutions. However, in the case of methylated borazines, the delocalization energy is responsible for the stabilization of F⁻ ion complexes. The N-trifluoroborazine showed much higher fluoride ion affinity (30.9 kcal/mol) in aqueous phase than the simple borazine.

Topics: Boron; Boron Compounds; Chlorine; Computer Simulation; Fluorides; Fluorine; Kinetics; Models, Molecular; Quantum Theory; Thermodynamics; Water; Water Pollutants, Chemical

Ab initio equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) calculations have been performed to investigate substituent effects on coupling constants for borazine and selected substituted borazines. For molecules in which F atoms are not bonded to adjacent atoms in the ring, F substitution increases the one-bond (11)B-(15)N coupling constants involving the atom at which substitution occurs but leaves the remaining one-bond B-N coupling constants essentially unchanged. For these molecules, the magnitudes of one-bond B-N coupling constants are only slightly dependent on the number of F atoms present. Fluorine substitution at adjacent B and N atoms in the borazine ring further increases the one-bond B-N coupling constant involving the substituted atoms and has the same effect on the other one-bond coupling constants as observed for corresponding molecules in which substitution occurs at alternate sites. In contrast to the effect of F substitution, substitution of Li at either N or B decreases one-bond B-N coupling constants relative to borazine. The effects of F and Li substitution on one-bond B-N coupling constants for borazine are similar to F and Li substitution effects on (13)C-(13)C coupling constants for benzene.

Topics: Benzene; Boron; Boron Compounds; Computer Simulation; Isotopes; Lithium; Molecular Structure; Nitrogen