DIANION DIALKALI METALS OF 2,2',5,5'-TETRASILABICYCLOPENTYLIDENE - SYNTHESIS AND CRYSTAL-STRUCTURES

被引:25
作者
SEKIGUCHI, A
ICHINOHE, M
KABUTO, C
SAKURAI, H
机构
[1] TOHOKU UNIV, FAC SCI, ORGANOSILICON RES LAB, AOBA KU, SENDAI, MIYAGI 980, JAPAN
[2] TOHOKU UNIV, FAC SCI, DEPT CHEM, AOBA KU, SENDAI, MIYAGI 980, JAPAN
关键词
D O I
10.1246/bcsj.68.2981
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The intramolecular bissilylation of 3,3,6,6,7,7,10,10-octamethyl-3,6,7,10-tetrasilacyclodecyne (4a) at 110 degrees 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 degrees for 6b.
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页码:2981 / 2988
页数:8
相关论文
共 45 条
  • [1] Ballard D., 1969, PURE APPL CHEM, V19, P449
  • [2] DISTORTED MOLECULES - PERTURBATION DESIGN, PREPARATION AND STRUCTURES
    BOCK, H
    RUPPERT, K
    NATHER, C
    HAVLAS, Z
    HERRMANN, HF
    ARAD, C
    GOBEL, I
    JOHN, A
    MEURET, J
    NICK, S
    RAUSCHENBACH, A
    SEITZ, W
    VAUPEL, T
    SOLOUKI, B
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1992, 31 (05) : 550 - 581
  • [3] STRUCTURES OF PERTURBED PI-SYSTEMS .3. TETRAPHENYLETHYLENEDISODIUM - THE BAND-STRUCTURE OF THE CC SINGLY BONDED, TWISTED (C6H5)2C CARBANIONS
    BOCK, H
    RUPPERT, K
    FENSKE, D
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1989, 28 (12): : 1685 - 1688
  • [4] CATALYTIC LITHIATION OF 1-OLEFINS
    BOGDANOVIC, B
    WERMECKES, B
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1981, 20 (08): : 684 - 686
  • [5] POLYHALO-ORGANOMETALLIC AND -ORGANOMETALLOIDAL COMPOUNDS .15. SOME REACTIONS OF HEXABROMOBENZENE
    BRENNAN, T
    GILMAN, H
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1968, 11 (03) : 625 - &
  • [7] TWISTING IN THE TETRAPHENYLETHYLENE DIANION
    FOX, MA
    SHULTZ, D
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (18) : 4386 - 4390
  • [8] GEOMETRY OF TETRAPHENYLETHYLENE DIANION
    GARST, JF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (23) : 6312 - &
  • [9] MODERN NMR-SPECTROSCOPY OF ORGANO-LITHIUM COMPOUNDS
    GUNTHER, H
    MOSKAU, D
    BAST, P
    SCHMALZ, D
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1987, 26 (12): : 1212 - 1220
  • [10] HOMMES NJRV, 1988, ANGEW CHEM INT EDIT, V27, P1083