Dianion Dialkali Metals of 2,2′,5,5′-Tetrasilabicyclopentylidene. Synthesis and Crystal Structures

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  • Akira Sekiguchi
    Department of Chemistry and Organosilicon Research Laboratory, Faculty of Science, Tohoku UniversityAoba-ku, Sendai 980-77
  • Masaaki Ichinohe
    Department of Chemistry and Organosilicon Research Laboratory, Faculty of Science, Tohoku UniversityAoba-ku, Sendai 980-77
  • Chizuko Kabuto
    Department of Chemistry and Organosilicon Research Laboratory, Faculty of Science, Tohoku UniversityAoba-ku, Sendai 980-77
  • Hideki Sakurai
    Department of Chemistry and Organosilicon Research Laboratory, Faculty of Science, Tohoku UniversityAoba-ku, Sendai 980-77

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<jats:title>Abstract</jats:title> <jats:p>The intramolecular bissilylation of 3,3,6,6,7,7,10,10-octamethyl-3,6,7,10-tetrasilacyclodecyne (4a) at 110 °C with a catalyst of Pd(OAc)2/1,1,3,3-tetramethylbutyl isocyanide under 5000 bar produced 2,2,2′,2′,5,5,5′,5′ -octamethyl-2,2′,5,5′-tetrasilabicyclopentylidene (5a). 2,2,2′,2′,5,5,5′,5′ -Octamethyl-2,2′,5,5′-tetragermabicyclopentylidene (5b) was also synthesized by the same method. The reaction of 5a with alkali metals (Li, Na, K, Rb, and Cs) in THF gave the corresponding dianion dialkali metals. The structures of 5a, (2,2,2′,2′,5,5,5′,5′-octamethyl-2,2′,5,5′-tetrasilabicyclopentylidene)bis[(tetrahydrofuran)lithium(I)] (6a), and (2,2,2′,2′,5,5,5′,5′-octamethyl-2,2′,5,5′ -tetrasilabicyclopentylidene)bis[(tetrahydrofuran)sodium(I)] (6b) were studied by X-ray crystallography as well as NMR spectroscopic means. The central anionic C–C bond is not twisted for 6a, whereas it is twisted by 17.1° for 6b.</jats:p>

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