title: Complexes of monocationic Group 13 elements with pentaphospha- and pentaarsaferrocene.
abstract: Reactions of the sandwich complexes [Cp*Fe(η(5)-E5)] (Cp*=η(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(μ,η(5):η(1 -E5 FeCp*)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 η(5)-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{(η(5)-As5)FeCp*}3][FAl] (5) without any σ-interactions of the As5-ring is obtained. All products are readily soluble in CH2 Cl2 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 (31)P{(1)H} magic-angle spinning (MAS) NMR spectra of 3 a-c are presented and the first crystal structure of the starting material 2 was determined.
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.
authors.forename: Martin
authors.initials: M
authors.lastname: Fleischmann
authors.forename: Stefan
authors.initials: S
authors.lastname: Welsch
authors.forename: Hannes
authors.initials: H
authors.lastname: Krauss
authors.forename: Monika
authors.initials: M
authors.lastname: Schmidt
authors.forename: Michael
authors.initials: M
authors.lastname: Bodensteiner
authors.forename: Eugenia V
authors.initials: EV
authors.lastname: Peresypkina
authors.forename: Marek
authors.initials: M
authors.lastname: Sierka
authors.forename: Christian
authors.initials: C
authors.lastname: Gröger
authors.forename: Manfred
authors.initials: M
authors.lastname: Scheer
mesh_terms: D001151:Arsenic / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry*; D005708:Gallium / Q000737:chemistry; D007204:Indium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D013793:Thallium / Q000737:chemistry
chemical_list: D002412:Cations; D005296:Ferrous Compounds; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D007204:Indium; D013793:Thallium; D005708:Gallium; D001151:Arsenic
keywords: NMR spectroscopy; X-ray diffraction; arsenic; phosphorus; sandwich complexes