Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids |
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| Authors: | Veronika Heinl Gbor Balzs Sarah Koschabek Maria Eckhardt Martin Piesch Michael Seidl Manfred Scheer |
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| Institution: | Faculty for Chemistry and Pharmacy, Institute of Inorganic Chemistry, University of Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany; (V.H.); (G.B.); (S.K.); (M.E.); (M.P.); (M.S.) |
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| Abstract: | The functionalization of the arsenic transfer reagent Cp″2Zr(η1:1-As4)] (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″2Zr(µ,η1:1:1:1-As4)(LA)] (LA = Fe(CO)4 (4); B(C6F5)3 (7)) and Cp″2Zr(µ,η3:1:1-As4)(Fe(CO)3)] (5) or a di-substitution Cp″2Zr(µ3,η1:1:1:1-As4)(LA)2] (LA = W(CO)5 (2); CpMn(CO)2 (3); AlR3 (6, R = Me, Et, iBu)) are monitored. In contrast to other coordination products, 5 shows an η3 coordination in which the butterfly As4 ligand is rearranged to a cyclo-As4 ligand. The reported complexes are rationalized in terms of inverse coordination. |
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| Keywords: | arsenic coordination chemistry DFT calculations Lewis acids zirconium |
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