Schön Florian, Sigmund Lukas M, Schneider Friederike, Hartmann Deborah, Wiebe Matthew A, Manners Ian, Greb Lutz
Department of Chemistry, University of Victoria, Victoria, BC, V8P 5C2, Canada.
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202202176. doi: 10.1002/anie.202202176. Epub 2022 Mar 29.
High molar weight polyphosphinoboranes represent materials with auspicious properties, but their preparation requires transition metal-based catalysts. Here, calix[4]pyrrolato aluminate is shown to induce the dehydropolymerization of phosphine boranes to high molar mass polyphosphinoboranes (up to M =43 000 Da). Combined GPC and P DOSY NMR spectroscopic analyses, quantum chemical computations, and stoichiometric reactions disclose a P-H bond activation by the cooperative action of the square-planar aluminate and the electron-rich ligand framework. This first transition metal-free catalyst for P-B dehydrocoupling overcomes the problem of residual d-block metal impurities in the resulting polymers that might interfere with the reproducibility of the properties for this emerging class of inorganic materials.
高分子量聚磷硼烷是具有优良性能的材料，但其制备需要基于过渡金属的催化剂。在此，杯[4]吡咯铝酸盐被证明可诱导膦硼烷脱水聚合成高分子量聚磷硼烷（分子量高达M = 43000 Da）。结合凝胶渗透色谱（GPC）和磷扩散排序核磁共振（P DOSY NMR）光谱分析、量子化学计算以及化学计量反应表明，平面正方形铝酸盐和富电子配体骨架的协同作用可实现P-H键活化。这种用于P-B脱氢偶联的首个无过渡金属催化剂克服了所得聚合物中残留d族金属杂质的问题，这些杂质可能会干扰这类新兴无机材料性能的可重复性。
