Complexes of Monocationic Group 13 Elements with Pentaphospha‐ and Pentaarsaferrocene. Issue 13 (24th February 2014)

• Record Type: Journal Article
• Authors: Fleischmann, Martin; Welsch, Stefan; Krauss, Hannes; Schmidt, Monika; Bodensteiner, Michael; Peresypkina, Eugenia V.; Sierka, Marek; Gröger, Christian; Scheer, Manfred
• Is Part Of: Chemistry. Volume 20:Issue 13(2014)
• Page Start: 3759
• Page End: 3768
• Publication Date: 2014-02-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201304466
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Reactions of the sandwich complexes [Cp*Fe(η<sup>5</sup>‐E<sub>5</sub>)] (Cp*=η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>; E=P (<bold>1</bold>), As (<bold>2</bold>)) with the monovalent Group 13 metals Tl<sup>+</sup>, In<sup>+</sup>, and Ga<sup>+</sup> containing the weakly coordinating anion [TEF] ([TEF]=[Al{OC(CF<sub>3</sub>)<sub>3</sub>}<sub>4</sub>]<sup>−</sup>) are described. Here, the one‐dimensional coordination polymers [M(μ, η<sup>5</sup>:η<sup>1</sup>‐E<sub>5</sub>FeCp*)<sub>3</sub>]<sub><italic>n</italic></sub>[TEF]<sub><italic>n</italic></sub> (E=P, M=Tl (<bold>3 a</bold>), In (<bold>3 b</bold>), Ga (<bold>3 c</bold>); E=As, M=Tl (<bold>4 a</bold>), In (<bold>4 b</bold>)) 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 η<sup>5</sup>‐bound E<sub>5</sub> 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 <bold>4 a</bold> for the larger [FAl] anion ([FAl]=[FAl{OC<sub>6</sub>F<sub>10</sub>(C<sub>6</sub>F<sub>5</sub>)}<sub>3</sub>]<sup>−</sup>), the coordination compound [Tl{(η<sup>5</sup>‐As<sub>5</sub>)FeCp*}<sub>3</sub>][FAl] (<bold>5</bold>) without any σ‐interactions of the As<sub>5</sub>‐ring is obtained. All products are readily soluble in CH<sub>2</sub>Cl<sub>2</sub> 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 <sup>31</sup>P{<sup>1</sup>H} magic‐angle spinning (MAS) NMR spectra of <bold>3 a–c</bold> are presented and the first crystal structure of the starting material <bold>2</bold> was determined.</p> </abstract>