Zusammenfassung
The functionalization of the arsenic transfer reagent [Cp '' Zr-2(eta(1:1)-As-4)] (1) focuses on modifying its properties and enabling a broader scope of reactivity. The coordination behavior of 1 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 ...
Zusammenfassung
The functionalization of the arsenic transfer reagent [Cp '' Zr-2(eta(1:1)-As-4)] (1) focuses on modifying its properties and enabling a broader scope of reactivity. The coordination behavior of 1 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-2(mu,eta(1:1:1:1)-As-4)(LA)] (LA = Fe(CO)(4) (4); B(C6F5)(3) (7)) and [Cp '' Zr-2(mu,eta(3:1:1)-As-4)(Fe(CO)(3))] (5) or a di-substitution [Cp '' Zr-2(mu(3),eta(1:1:1:1)-As-4)(LA)(2)] (LA = W(CO)(5) (2); CpMn(CO)(2) (3); AlR3 (6, R = Me, Et, Bu-i)) are monitored. In contrast to other coordination products, 5 shows an eta(3) coordination in which the butterfly As-4 ligand is rearranged to a cyclo-As-4 ligand. The reported complexes are rationalized in terms of inverse coordination.
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