Hlina Johann, Baumgartner Judith, Marschner Christoph, Zark Patrick, Müller Thomas
Institut für Anorganische Chemie, Technische Universität Graz , Stremayrgasse 9, 8010 Graz, Austria.
Organometallics. 2013 Jun 10;32(11):3300-3308. doi: 10.1021/om400215v. Epub 2013 May 17.
Reaction of the PEt adduct of a disilylated five-membered cyclic germylene with group 4 metallocene dichlorides in the presence of magnesium led to the formation of the respective germylene metallocene phosphine complexes of titanium, zirconium, and hafnium. Attempts to react the related NHC adduct of a disilylated four-membered cyclic germylene under the same conditions with CpTiCl did not give the expected germylene NHC titanocene complex. This complex was, however, obtained in the reaction of CpTi(btmsa) with the NHC germylene adduct. A computational analysis of the structure of the group 4 metallocene germylene complexes revealed the multiple-bond character of the M-Ge(II) linkage, which can be rationalized with the classical σ-donor/π-acceptor interaction. The strength of the M-Ge(II) bond increases descending group 4.
在镁存在的情况下，二硅基化五元环状亚锗烯的PEt加合物与第4族金属茂二氯化物反应，生成了钛、锆和铪各自的亚锗烯金属茂膦配合物。尝试使二硅基化四元环状亚锗烯的相关NHC加合物在相同条件下与CpTiCl反应，未得到预期的亚锗烯NHC钛茂配合物。然而，该配合物是在CpTi(btmsa)与NHC亚锗烯加合物的反应中得到的。对第4族金属茂亚锗烯配合物结构的计算分析揭示了M-Ge(II)键的多重键特征，这可以用经典的σ供体/π受体相互作用来解释。第4族中，M-Ge(II)键的强度自上而下增加。
