García-Romero Álvaro, Hu Chenyang, Pink Maren, Goicoechea Jose M
Department of Chemistry, Indiana University, 800 East Kirkwood Ave., Bloomington, Indiana 47405, United States.
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Rd., Oxford OX1 3TA, U.K.
J Am Chem Soc. 2025 Jan 8;147(1):1231-1239. doi: 10.1021/jacs.4c15041. Epub 2024 Dec 19.
The synthesis and isolation of TerP═GaTer and TerP═InTer (Ter = 2,6-Dipp-CH; Dipp = 2,6-diisopropylphenyl) is reported. These compounds feature unsupported P═Ga and P═In double bonds and two-coordinate triel element centers. Key to the stabilization of such compounds is the steric bulk of the terphenyl substituents, which serve to shield the highly reactive P═E bonds (E = Ga, In) and prevent further aggregation. When smaller aromatic substituents are employed on the phosphorus-containing precursor, the cyclic compounds MesP(ETer) (Mes = 2,4,6-Bu-CH) are isolated instead. These species contain weakly aromatic three-membered rings. The presence of an external base (PMe) is required in order to stabilize a phosphagallene when the smaller Mes* substituent is used, allowing for the isolation of Mes*P═GaTer(PMe).
报道了TerP═GaTer和TerP═InTer（Ter = 2,6 - Dipp - CH；Dipp = 2,6 - 二异丙基苯基）的合成与分离。这些化合物具有未配位的P═Ga和P═In双键以及二配位的三价元素中心。此类化合物稳定的关键在于三联苯取代基的空间位阻，其用于屏蔽高反应性的P═E键（E = Ga，In）并防止进一步聚集。当在含磷前体上使用较小的芳基取代基时，会分离出环状化合物MesP(ETer)（Mes = 2,4,6 - Bu - CH）。这些物种含有弱芳香性的三元环。当使用较小的Mes取代基时，为了稳定磷杂镓烯需要外部碱（PMe）的存在，从而得以分离出MesP═GaTer(PMe)。
