Synthesis and Characterization of Heteroleptic 1‑Tris(pyrazolyl)borate Beryllium Complexes

The synthesis and crystal structures of 1-tris­(pyrazolyl)­borate beryllium halides TpBeX (X = Cl 1, Br 2, I 3, F 4), the pyrazole adduct of TpBeF (5) and of 1-tris­(pyrazolyl)­borate beryllium hydride, deuteride and azide TpBeX (X = H 6, 2H (D) 7, N3 8; Tp = 1-trispyrazolylborate) is described. In addition, 9Be-NMR spectroscopy is introduced as suitable analytical tool for the in situ characterization of heteroleptic organoberyllium halides, pseudohalides and hydrides. Studies in different solvents and solvent mixtures allowed the formulation of a reference guide for the chemical shift of heteroleptic coordination complexes of beryllium only based on variation of the second substituent.本文报道了1-三(吡唑基)硼酸根卤化铍TpBeX（X=Cl 1、Br 2、I 3、F 4）、TpBeF的吡唑加合物（5）以及1-三(吡唑基)硼酸根氢化铍、氘化铍和叠氮化铍TpBeX（X=H 6、²H(D) 7、N3 8；其中Tp为三(吡唑基)硼酸根（1-trispyrazolylborate））的合成与晶体结构。此外，铍-9核磁共振波谱法（9Be-NMR）被确立为适用于异配有机铍卤化物、拟卤化物及氢化物原位表征的有效分析工具。通过在不同溶剂及溶剂混合物中开展的系统研究，我们建立了一套仅基于第二取代基变化的铍异配配位配合物化学位移参考指南。