Institute of Inorganic Chemistry, University of Regensburg, 93053, Regensburg, Germany.
Chemistry. 2023 Jun 19;29(34):e202301016. doi: 10.1002/chem.202301016. Epub 2023 May 2.
The functionalization of the polypnictogen ligand complexes [Cp'' Zr(η -E )] (E=P (1 a), As (1 b); Cp''=1,3-di-tertbutyl-cyclopentadienyl) is focused to modify the features of the polypnictogen unit to explore new synthetic pathways for further transformations. The reaction behavior of 1 towards main group nucleophiles is investigated. The reaction of 1 a with BuLi leads to the ionic product Li[Cp'' Zr(η -P Bu)] (2) where an organic group is attached to a bridgehead phosphorus atom of the butterfly unit. Further reactions of 2 with quenching electrophilic reagents enable the introduction of other substituents. Moreover, a condensation of 2 to [(Cp'' Zr) (μ,η -P Bu )] (3), containing a novel P -unit, has been observed. The reaction of 1 with LiNMe and LiCH SiMe leads to a partial fragmentation of the E unit and the compounds [Cp'' Zr(η -E Nu)] (Nu=NMe : E=P (6 a), As (6 b); Nu=CH SiMe : E=P (7 a), As (7 b)) are formed.
聚杂化配体配合物[Cp''Zr(η-E)]（E=P（1a），As（1b）；Cp''=1,3-二叔丁基环戊二烯基）的功能化侧重于修饰聚杂化单元的特征，以探索进一步转化的新合成途径。研究了 1 对主族亲核试剂的反应行为。1a 与 BuLi 的反应得到离子产物 Li[Cp''Zr(η-P Bu)]（2），其中一个有机基团连接到蝶形单元的桥头磷原子上。进一步用猝灭亲电试剂与 2 反应可引入其他取代基。此外，还观察到 2 缩合生成含有新型 P 单元的[(Cp''Zr)(μ,η-P Bu)]（3）。1 与 LiNMe 和 LiCH SiMe 的反应导致 E 单元部分断裂，形成化合物[Cp''Zr(η-E Nu)]（Nu=NMe：E=P（6a），As（6b）；Nu=CH SiMe：E=P（7a），As（7b））。
