Complexes of Monocationic Group 13 Elements with Pentaphospha‐ and Pentaarsaferrocene |
| |
| Authors: | Martin Fleischmann Dr. Stefan Welsch Dr. Hannes Krauss Monika Schmidt Dr. Michael Bodensteiner Dr. Eugenia V. Peresypkina Prof. Dr. Marek Sierka Dr. Christian Gröger Prof. Dr. Manfred Scheer |
| |
| Affiliation: | 1. Institut für Anorganische Chemie, Universit?t Regensburg, 93040 Regensburg (Germany), Fax: (+49)?941‐943‐4439;2. Nikolaev Institute of Inorganic Chemistry SB RAS, Ak. Lavrentiev pr. 3, 630090 Novosibirsk (Russia);3. Otto‐Schott‐Institut für Materialforschung, Friedrich‐Schiller‐Universit?t Jena, 07743 Jena (Germany);4. Institut für Biophysik und Physikalische Biochemie, Universit?t Regensburg, 93040 Regensburg (Germany) |
| |
| 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. |
| |
| Keywords: | arsenic NMR spectroscopy phosphorus sandwich complexes X‐ray diffraction |
|
|
