LaPierre Etienne A, Patrick Brian O, Manners Ian
Department of Chemistry, University of Victoria, 3800 Finnerty Rd, Victoria, British Columbia V8P 5C2, Canada.
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
J Am Chem Soc. 2023 Apr 5;145(13):7107-7112. doi: 10.1021/jacs.3c01942. Epub 2023 Mar 24.
We report the synthesis of the monomeric phosphaborene ArP═B(TMP) () (Ar = 2,6-bis(triisopropylphenyl)-3,5-diisopropylphenyl) containing 2-coordinate phosphorus and boron centers. Compound has a PB bond length of 1.741(3) Å, the shortest reported to date. Computational examination of the bonding in reveals, in addition to the σ bond, the presence of a single classical π bond and a large Wiberg bond index of 1.9707, consistent with double bond, and not triple bond, character. The chemistry of is marked by its low reactivity, which is rationalized by examination of the frontier molecular orbitals and steric considerations.
我们报道了含二配位磷和硼中心的单体磷硼烯ArP═B(TMP)（）（Ar = 2,6-双（三异丙基苯基）-3,5-二异丙基苯基）的合成。化合物的PB键长为1.741(3) Å，是迄今为止报道的最短键长。对该化合物键合的计算研究表明，除了σ键外，还存在一个经典的π键且维伯格键指数高达1.9707，这与双键而非三键特征相符。该化合物的化学性质以其低反应活性为特点，通过对前沿分子轨道和空间因素的研究可对此作出合理解释。
