Institute of Inorganic Chemistry, Division Molecular Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany.
Chemistry. 2019 Sep 18;25(52):12206-12213. doi: 10.1002/chem.201902681. Epub 2019 Aug 23.
The influence of substituents on α-borylated phosphorus ylides (α-BCPs) has been investigated in a combined experimental and quantum chemical approach. The synthesis and characterization of Me PC(H)B(iBu) (1), consisting of small Me substituents on phosphorous and iBu residues on boron, is reported. Compound 1 is accessible through a novel synthetic approach, which has been further elucidated through DFT studies. The reactivity of 1 towards various small molecules was probed and compared with that of a previously published derivative, Ph PC(Me)BEt (2). Both α-BCPs react with NH to undergo heterolytic N-H bond cleavage. Different di- and trimeric ring structures were observed in the reaction products of 1 with CO and CO . With PhNCO and PHNCS, the expected insertion products [Me PC(H)(PhNCO)B(iBu) ] and [Me PC(H)(PhNCS)B(iBu) ], respectively, were isolated.
采用实验和量子化学相结合的方法研究了取代基对α-硼代磷叶立德（α-BCP）的影响。报道了由磷上的小 Me 取代基和硼上的 iBu 残基组成的 Me PC(H)B(iBu)（1）的合成和表征。通过一种新的合成方法得到了化合物 1，通过 DFT 研究进一步阐明了该方法。研究了 1 与各种小分子的反应性，并与先前报道的衍生物 Ph PC(Me)BEt（2）进行了比较。两种 α-BCP 都与 NH 反应，经历异裂 N-H 键断裂。在 1 与 CO 和 CO 的反应产物中观察到不同的二聚体和三聚体环结构。与 PhNCO 和 PHNCS 反应，分别分离得到预期的插入产物[Me PC(H)(PhNCO)B(iBu) ]和[Me PC(H)(PhNCS)B(iBu) ]。
