Improved Access to {[ω‐(Phosphanyl)alkyl]cyclopentadienyl}cobalt(I) Complexes: Decomplexation of the Phosphane Arm; Alkyne Complexes; Synthesis of Mononuclear Vinylidenecobalt(I) Complexes
作者:Jan Foerstner、Ralf Kettenbach、Richard Goddard、Holger Butenschön
DOI:10.1002/cber.19961290312
日期:1996.3
phosphane arm at room temperature with formation of 7, 5, 6, 8. The ethene ligand in 4 can be replaced by alkynes under equally mild reaction conditions (formation of 9, 11 – 16). The reaction with ethyne results in the formation of vinylidene complex 10. The yields of the reactions with nonaromatic alkynes could be improved by treating 3 with the alkyne in the presence of sodium amalgam. The unsubstituted
提出了[(2-膦酰基乙基)环戊二烯基]钴(I)螯合物的改进的合成方法,其中顺磁性氯化物3是乙烯络合物4的前体。后者容易发生配体交换反应,在双齿试剂(1,5-环辛二烯,1,2-双(二异丙基膦基)乙烷,2,2'-联吡啶,降冰片二烯)的情况下,会导致膦烷臂在室温下形成7、5、6、8。在同样温和的反应条件下(9,11 – 16的形成),炔烃可以代替4中的乙烯配体。与乙炔的反应导致亚乙烯基配合物10的形成。与非芳族炔烃的反应产率可以通过在钠汞齐存在下用炔烃处理3来提高。通过该途径,分别以38%和40%的产率获得未取代的亚乙烯基络合物10及其叔丁基衍生物17。