Fleischmann, Martin and Welsch, Stefan and Krauss, Hannes and Schmidt, Monika and Bodensteiner, Michael and Peresypkina, Eugenia V. and Sierka, Marek and Groeger, Christian and Scheer, Manfred (2014) Complexes of Monocationic Group 13 Elements with Pentaphospha- and Pentaarsaferrocene. CHEMISTRY-A EUROPEAN JOURNAL, 20 (13). pp. 3759-3768. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Reactions of the sandwich complexes [Cp*Fe((5)-E-5)] (Cp*=(5)-C5Me5; E=P (1), As (2)) with the monovalent Group 13 metals Tl+, In+, and Ga+ containing the weakly coordinating anion [TEF] ([TEF]=[Al{OC(CF3)(3)}(4)](-)) are described. Here, the one-dimensional coordination polymers [M(,(5):(1)-E5FeCp*)(3)](n)[TEF](n) (E=P, M=Tl (3a), In (3b), Ga (3c); E=As, M=Tl (4a), In (4b)) are obtained as sole products in good yields. All products were analyzed by single-crystal X-ray diffraction, revealing a similar assembly of the products with (5)-bound E-5 ligands and very weak sigma-interactions between one P or As atom of the ring to the neighbored Group 13 metal cation. By exchanging the [TEF] anion of 4a for the larger [FAl] anion ([FAl]=[FAl{OC6F10(C6F5)}(3)](-)), the coordination compound [Tl{((5)-As-5)FeCp*}(3)][FAl] (5) without any sigma-interactions of the As-5-ring is obtained. All products are readily soluble in CH2Cl2 and exhibit a dynamic coordination behavior in solution, which is supported by NMR spectroscopy and ESI-MS spectrometry as well as by osmometric molecular-weight determination. For a better understanding of the proceeding equilibrium DFT calculations of the cationic complexes were performed for the gas phase and in solution. Furthermore, the P-31{H-1} magic-angle spinning (MAS) NMR spectra of 3a-c are presented and the first crystal structure of the starting material 2 was determined.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | WEAKLY COORDINATING ANIONS; N-LIGAND COMPLEXES; UNIVALENT GALLIUM; SILVER(I) CATIONS; DYNAMIC-BEHAVIOR; BUILDING-BLOCKS; BASIC SOLUTION; BASIS-SETS; CHEMISTRY; MOLECULES; arsenic; NMR spectroscopy; phosphorus; sandwich complexes; X-ray diffraction |
| Subjects: | 500 Science > 540 Chemistry & allied sciences 500 Science > 570 Life sciences |
| Divisions: | Biology, Preclinical Medicine > Institut für Biophysik und physikalische Biochemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 15 Nov 2019 13:41 |
| Last Modified: | 15 Nov 2019 13:41 |
| URI: | https://pred.uni-regensburg.de/id/eprint/10454 |
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