Boryl Anions Research Articles

A systematic study of the stabilities of cyclic boryl anions

In this study, we perform several DFT functionals and post-SCF methods (MP2 and CCSD(T)) to investigate the stability of a series of virtual cyclic boryl anions. This investigation stems from two aspects: (1) the energetic difference between S(0) and T(1) states and (2) the electron affinity of the cyclic boryl anions. The results are systematically discussed in terms of substitution effect, influence of the steric effect, number of nitrogen atoms, the ring size and solvation inclusion. Moreover, the effect of the counter cation Li(+) on the singlet-triplet splitting is also investigated. Among various boryl anions studied, the results predict bulky-group substituted 5i and 8, shown in Schemes 3 and 4, respectively, to be stable anions in gas phase as well as in organic solvents. Since boryl anions may be exploited to synthesize new boron-containing compounds as well as to provide synthetic routes different from traditional protocols, the predicted thermodynamically stable 5i and 8 are then of both synthetic interest and challenging for future applications of cyclic boryl anions.

ChemInform Abstract: Recent Developments of Boryl Anions: Boron Analogues of Carbanion.

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Recent Developments of Boryl Anions: Boron Analogues of Carbanion

Abstract This account reviews the chemistry of “boryl anion.” Boryl anions can be classified with their metallic counterpart, such as Li, Mg, Cu, and Zn in a similar manner to the classification of carbanions. The early attempts to generate boryl anions by reductive dehalogenation of haloboranes with alkali metal or photolysis of tetraphenylborate compounds had no modern spectroscopic identification of the reactive “boryl anion.” Recent developments of base-stabilized boryl anion, base–BH2−M+ (base = NEt3 or PCy3, M=K or Li), and generation of borylcopper species, “pinBCuL,” have opened a new area of organoboron chemistry. Recently, we have synthesized a lithium salt of boryl anion, boryllithium, which reacted with electrophiles as a boron nucleophile. Based on the high reactivity of boryllithium, transmetallation to other metals enables synthesis of a series of borylmetals, such as borylmagnesium, borylcopper, and borylzinc species. All of these compounds were isolated and structurally characterized to have an sp2 boron atom. Reactivity with organic electrophiles could confirm that they behaved as boron nucleophiles.

A Computational Study on the Kinetic Stability of Cyclic Boryl Anions~!2007-12-13~!2008-05-13~!2008-06-11~!

A Computational Study on the Kinetic Stability of Cyclic Boryl Anions~!2007-12-13~!2008-05-13~!2008-06-11~!