Duetsch, Luis and Fleischmann, Martin and Welsch, Stefan and Balazs, Gabor and Kremer, Werner and Scheer, Manfred (2018) Dicationic E-4 Chains (E = P, As, Sb, Bi) Embedded in the Coordination Sphere of Transition Metals. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57 (12). pp. 3256-3261. ISSN 1433-7851, 1521-3773
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The oxidation chemistry of the complexes [{CpMo(CO)(2)}(2)(mu,eta(2):eta(2)-E-2)] (E=P (A), As (B), Sb (C), Bi (D)) is compared. The oxidation of A-D with [Thia](+) (=[C12H8S2](+)) results in the selective formation of the dicationic E-4 complexes [{CpMo(CO)(2)}(4)(mu(4),eta(2):eta(2):eta(2):eta(2)-E-4)](2+) (E=P (1), As (2), Sb (3), Bi (4)), stabilized by four [CpMo(CO)(2)] fragments. The formation of the corresponding monocations [A](+), [C](+), and [D](+) could not be detected by cyclic voltammetry, EPR, or NMR spectroscopy. This finding suggests that dimerization is fast and that there is no dissociation in solution, which was also predicted by DFT calculations. However, EPR measurements of 2 confirmed the presence of small amounts of the radical cation [B](+) in solution. Single-crystal X-ray diffraction revealed that the products 1 and 2 feature a zigzag E-4 chain in the solid state while 3 and 4 bear a central E-4 cage with a distorted "butterfly-like" geometry. Additionally, 1 can be easily and reversibly converted into a symmetric and an unsymmetric form.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MAIN-GROUP; LIGAND COMPLEXES; WHITE PHOSPHORUS; DEVELOPING-AREA; CHEMISTRY; CATIONS; ELEMENT; PENTAPHOSPHAFERROCENE; HEXAPHOSPHABENZENE; POLYARSENIDES; catenation; cationic frameworks; oxidation chemistry; polypnictogen units; weakly coordinating anions |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Mar 2020 09:08 |
| Last Modified: | 12 Mar 2020 09:08 |
| URI: | https://pred.uni-regensburg.de/id/eprint/14898 |
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