Heinl Veronika, Balázs Gábor, Koschabek Sarah, Eckhardt Maria, Piesch Martin, Seidl Michael, Scheer Manfred
Faculty for Chemistry and Pharmacy, Institute of Inorganic Chemistry, University of Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany.
Molecules. 2021 May 17;26(10):2966. doi: 10.3390/molecules26102966.
The functionalization of the arsenic transfer reagent [Cp″Zr(η-As)] () focuses on modifying its properties and enabling a broader scope of reactivity. The coordination behavior of towards different Lewis-acidic transition metal complexes and main group compounds is investigated by experimental and computational studies. Depending on the steric requirements of the Lewis acids and the reaction temperature, a variety of new complexes with different coordination modes and coordination numbers could be synthesized. Depending on the Lewis acid (LA) used, a mono-substitution in [Cp″Zr(µ,η-As)(LA)] (LA = Fe(CO) (); B(CF) ()) and [Cp″Zr(µ,η-As)(Fe(CO))] () or a di-substitution [Cp″Zr(µ,η-As)(LA)] (LA = W(CO) (); CpMn(CO) (); AlR (, R = Me, Et, Bu)) are monitored. In contrast to other coordination products, shows an η coordination in which the butterfly As ligand is rearranged to a -As ligand. The reported complexes are rationalized in terms of inverse coordination.
砷转移试剂[Cp″Zr(η-As)]（）的功能化侧重于修饰其性质并实现更广泛的反应活性范围。通过实验和计算研究，研究了其与不同路易斯酸性过渡金属配合物和主族化合物的配位行为。根据路易斯酸的空间需求和反应温度，可以合成具有不同配位模式和配位数的多种新型配合物。根据所使用的路易斯酸（LA），监测了[Cp″Zr(µ,η-As)(LA)]（LA = Fe(CO)（）；B(CF)（））和[Cp″Zr(µ,η-As)(Fe(CO))]（）中的单取代或[Cp″Zr(µ,η-As)(LA)]（LA = W(CO)（）；CpMn(CO)（）；AlR（，R = Me，Et，Bu））中的双取代。与其他配位产物不同，显示出η配位，其中蝴蝶状As配体重排为-As配体。所报道的配合物根据逆配位进行了合理化解释。
