Fantuzzi Felipe, Chaer Nascimento Marco A
Departamento de Físico-Química, Instituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, A-412. Rio de Janeiro, RJ, 21941-909 (Brazil), Fax: (+55) 21-3938-7265.
Chemistry. 2015 May 18;21(21):7814-9. doi: 10.1002/chem.201500241. Epub 2015 Apr 2.
A class of polymeric compounds containing boron-boron triple bonds stabilized by N-heterocyclic biscarbenes is proposed. Since a triply bonded B2 is related to its third excited state, the predicted macromolecule would be composed by several units of an electronically excited first-row homonuclear dimer. Moreover, it is shown that the replacement of biscarbene with N2 or CO as spacers could change the bonding profile of the boron-boron units to a cumulene-like structure. Based on these results, different types of diboryne polymers are proposed, which could lead to an unprecedented set of boron materials with distinct physical properties. The novel diboryne macromolecules could be synthesized by the reaction of Janus-type biscarbenes with tetrabromodiborane, B2 Br4 , and sodium naphthalenide, [Na(C10 H8 )], similarly to Braunschweig's work on the room temperature stable boron-boron triple bond compounds (Science, 2012, 336, 1420).
提出了一类由 N-杂环双卡宾稳定的含硼硼三键的聚合化合物。由于三键合的 B₂ 与其第三激发态相关，预测的大分子将由几个电子激发的第一行同核二聚体单元组成。此外，研究表明，用 N₂ 或 CO 作为间隔基取代双卡宾会使硼硼单元的键合结构变为类累积烯结构。基于这些结果，提出了不同类型的二硼炔聚合物，这可能会导致出现一系列具有独特物理性质的前所未有的硼材料。新型二硼炔大分子可以通过 Janus 型双卡宾与四溴二硼烷（B₂Br₄）和萘钠（[Na(C₁₀H₈)]）反应合成，这与 Braunschweig 关于室温稳定的硼硼三键化合物的工作类似（《科学》，2012 年，336 卷，1420 页）。
