Schmidt, Monika and Konieczny, David and Peresypkina, Eugenia V. and Virovets, Alexander V. and Balazs, Gabor and Bodensteiner, Michael and Riedlberger, Felix and Krauss, Hannes and Scheer, Manfred (2017) Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56 (25). pp. 7307-7311. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The redox chemistry of [Cp*Fe(eta(5)-As-5)] (1, Cp* = eta(5)-C5Me5) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(eta(5)-P-5)]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel As-n scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme)(2)][{Cp*Fe(mu,eta(2:2)-As-2)}(2)] (2) and the arsenic-rich complexes [K(dme)(3)](2)[(Cp*Fe)(2)(mu,eta(4:4)-As-10)] (3), [K(dme)(2)](2)[(Cp*Fe)(2)(mu,eta(2:2:2:2)-As-14)] (4), and [K(dme)(3)](2)[(Cp*Fe)(4)(mu(4),eta(4:3:3:2:2:1:1)-As-18)] (5). Compound 4 and the poly-arsenide complex 5 are the largest anionic As-n ligand complexes reported thus far. Complexes 2-5 were characterized by single-crystal X-ray diffraction, H-1 NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(eta(5)-As-5)](-), which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe)(2)(mu,eta(4:4)-As-10)](2-).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CRYSTAL-STRUCTURE; ELECTRON-DIFFRACTION; COMPLEXES; CHEMISTRY; PENTAPHOSPHAFERROCENE; FERROCENE; LIGANDS; ANIONS; DIMERIZATION; FULLERENE; arsenic; DFT calculations; iron; polyarsenides; reduction |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Dec 2018 13:10 |
| Last Modified: | 11 Feb 2019 13:20 |
| URI: | https://pred.uni-regensburg.de/id/eprint/701 |
Actions (login required)
 |
View Item |
