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The substitution chemistry of RuCp* (temeda)Cl

Substitutionsreaktionen von RuCp*(tmeda)Cl

  • Anorganische Und Physikalische Chemie
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Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Summary

Halide abstraction from RuCp*(tmeda)Cl (1,tmeda=Me2NCH2CH2NMe2) with NaBPh4 in CH2Cl2 leads to the formation of the sandwich complex RuCp*(η6-C6H5BPh3) (2). In the presence of CH3CN (1 equiv.) and CO, however, the cationic complexes [RuCp*(tmeda)(CH3CN)]+ (3) and [RuCp*(temeda)(CO)]+ (5) are obtained. In CH3CN,tmeda is also replaced giving [RuCp*(CH3CN)3]+ (4). Complex1 reacts readily with terminal acetylenes HC≡CR, the products depending on the nature ofR (Ph, SiMe3,n-Bu, COOEt). Thus, withR=Ph the ruthenacyclopentatriene complex RuCp*(σ,σ′-C4Ph2H2)Cl (6), withR=SiMe3 the cyclobutadiene complex Ru(Cp*)(σ4-C4H2(1,2-SiMe3)2)Cl (7), and withR=n-Bu and COOEt the binuclear complexes (Cp*)RuCl2(η2:η4-μ2-C4H2(1,3-R)2)Ru(Cp*) (8,9) are obtained. Furthermore, with diethyl maleate in the presence of 1 equiv. of LiCl,1 transforms into the new anionic complex Li[Ru(Cp*) (η2-C2H2(COOEt)2)Cl2] (10). X-ray structures of2,3,4,7, and10 are included.

Zusammenfassung

Chloridabspaltung von RuCp*(tmeda)Cl (1,tmeda=Me2NCH2CH2NMe2) mittels NaBPh4 in CH2Cl2 führt zur Bildung des Halbsandwich-Komplexes RuCp*(η6-C6H5BPh3) (2), während in Gegenwart von CH3CN oder CO die beiden kationischen Verbindungen [RuCp*(tmeda)(CH3CN)]+ (3) und [RuCp*(tmeda)(CO)]+ (5) entstehen. In CH3CN als Lösungsmittel wird sogartmeda unter Bildung von [RuCp*(CH3CN)3]+ (4) verdrängt. Komplex1 reagiert sehr leicht mit terminalen Alkinen HC≡CR, wobei die Produkte stark von der Natur des SubstituentenR (Ph, SiMe3,n-Bu, COOEt) abhängen. Im Fall vonR=Ph entsteht der Ruthenacyclopentatrien-Komplex RuCp*(σσ′-C4Ph2H2)Cl (6), mitR=SiMe3 der Cyclobutadien-Komplex Ru(Cp*)(η4-C4H2(1,2-SiMe3)2)Cl (7), und im Fall vonR=n-Bu und COOEt bilden sich die binuklearen Komplexe (Cp*)RuCl2(η2:η4-μ2-C4H2(1,3-R)2)Ru(Cp*) (8,9). Überdies reagiert1 mit Maleinsäurediethylester in Gegenwart von LiCl zum neuen anionischen Komplex Li[Ru(Cp*) (η2-C2H2(COOEt)2)Cl2] (10). Von2,3,4,7 und10 wurden die Kristallstrukturen bestimmt.

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Authors and Affiliations

  1. Institute of Inorganic Chemistry, Technical University of Vienna, A-1060, Vienna, Austria

    C. Gemel, A. LaPensée, K. Mauthner, R. Schmid & K. Kirchner

  2. Institute of Mineralogy, Crystallography, and Structural Chemistry, Technical University of Vienna, A-1060, Vienna, Austria

    K. Mereiter

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  1. C. Gemel
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  2. A. LaPensée
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  3. K. Mauthner
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  4. K. Mereiter
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  5. R. Schmid
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  6. K. Kirchner
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Gemel, C., LaPensée, A., Mauthner, K. et al. The substitution chemistry of RuCp* (temeda)Cl. Monatsh Chem 128, 1189–1199 (1997). https://doi.org/10.1007/BF00807250

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  • DOI: https://doi.org/10.1007/BF00807250

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