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- Title
Complexes of Monocationic Group 13 Elements with Pentaphospha- and Pentaarsaferrocene.
- Authors
Fleischmann, Martin; Welsch, Stefan; Krauss, Hannes; Schmidt, Monika; Bodensteiner, Michael; Peresypkina, Eugenia V.; Sierka, Marek; Gröger, Christian; Scheer, Manfred
- Abstract
Reactions of the sandwich complexes [Cp*Fe(η5-E5)] (Cp*=η5-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(μ,η5:η1-E5FeCp*)3] n[TEF] n (E=P, M=Tl ( 3 a), In ( 3 b), Ga ( 3 c); E=As, M=Tl ( 4 a), In ( 4 b)) 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 η5-bound E5 ligands and very weak σ-interactions between one P or As atom of the ring to the neighbored Group 13 metal cation. By exchanging the [TEF] anion of 4 a for the larger [FAl] anion ([FAl]=[FAl{OC6F10(C6F5)}3]−), the coordination compound [Tl{(η5-As5)FeCp*}3][FAl] ( 5) without any σ-interactions of the As5-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 31P{1H} magic-angle spinning (MAS) NMR spectra of 3 a-c are presented and the first crystal structure of the starting material 2 was determined.
- Subjects
MONOVALENT cations; ANIONS; POLYMERS; FERROCENE; X-ray diffraction; NUCLEAR magnetic resonance spectroscopy
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 13, p3759
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201304466