Suzuki Noriyuki, Aihara Naoto, Takahara Hidemichi, Watanabe Takaaki, Iwasaki Masakazu, Saburi Masahiko, Hashizume Daisuke, Chihara Teiji
RIKEN, Wako, Saitama 351-0198, Japan.
J Am Chem Soc. 2004 Jan 14;126(1):60-1. doi: 10.1021/ja0385742.
Five-membered metallacyclic alkynes that have no substituents adjacent to the triple bond have been synthesized, isolated, and structurally characterized. Zirconocene dichlorides, Cp'2ZrCl2 (Cp' = C5H5, C5H4-t-Bu), reacted with 1,4-dichlorobut-2-yne in the presence of magnesium to give 1-zirconacyclopent-3-yne compounds (5 (a) Cp' = C5H5, (b) Cp' = C5H4-t-Bu) that have a -CH2CCCH2- moiety in good yields. They are stable enough to be isolated in a pure form, despite the absence of substituents. 5a reacted with an equimolar amount of Cp2Zr(but-1-ene)(PMe3) to produce a bimetallic complex in which the zirconacyclopentyne coordinates to the other zirconocene moiety as an alkyne.
已合成、分离并对结构进行了表征的五元金属环炔，其叁键相邻无取代基。二氯二茂锆（Cp'2ZrCl2，Cp' = C5H5、C5H4-t-Bu）在镁存在下与1,4 - 二氯丁 - 2 - 炔反应，以良好产率生成具有-CH2CCCH2-部分的1 - 锆环戊 - 3 - 炔化合物（5（a）Cp' = C5H5，（b）Cp' = C5H4-t-Bu）。尽管没有取代基，它们仍足够稳定，可以以纯形式分离出来。5a与等摩尔量的Cp2Zr(丁 - 1 - 烯)(PMe3)反应生成一种双金属配合物，其中锆环戊炔作为炔烃与另一个二茂锆部分配位。
