研究 [Ge9]4- 对 [Fe(cot)(CO)3] 的反应活性：[Ge8Fe(CO)3]3- 和阴离子有机金属物种 [Fe(cot)(CO)3]- 的合成与表征。

Studies on the reactivity of [Ge9]4- towards [Fe(cot)(CO)3]: synthesis and characterization of [Ge8Fe(CO)3]3- and of the anionic organometallic species [Fe(cot)(CO)3]-.

机构信息

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA UK.

出版信息

Chemistry. 2010 Sep 24;16(36):11145-50. doi: 10.1002/chem.201000507.

DOI:10.1002/chem.201000507

PMID:20680939

Abstract

Reaction of cyclooctatetraene (COT) iron(II) tricarbonyl, [Fe(cot)(CO)(3)], with one equivalent of K(4)Ge(9) in ethylenediamine (en) yielded the cluster anion Ge(8)Fe(CO)(3) which was crystallographically-characterized as a K(2,2,2-crypt) salt in K(2,2,2-crypt)[Ge(8)Fe(CO)(3)]. The chemically-reduced organometallic species Fe(η(3)-C(8)H(8))(CO)(3) was also isolated as a side-product from this reaction as [K(2,2,2-crypt)][Fe(η(3)-C(8)H(8))(CO)(3)]. Both species were further characterized by EPR and IR spectroscopy and electrospray mass spectrometry. The Ge(8)Fe(CO)(3) cluster anion represents an unprecedented functionalized germanium Zintl anion in which the nine-atom precursor cluster has lost a vertex, which has been replaced by a transition-metal moiety.

摘要

环辛四烯铁(II)三羰基，[Fe(cot)(CO)(3)]，与一当量的 K(4)Ge(9)在乙二胺(en)中反应生成了簇阴离子[Ge(8)Fe(CO)(3)]，该阴离子通过结晶学方法被确认为[K(2,2,2-crypt)]盐，在K(2,2,2-crypt)[Ge(8)Fe(CO)(3)]中。化学还原的有机金属物种[Fe(η(3)-C(8)H(8))(CO)(3)]也作为副产物从该反应中被分离出来，为[K(2,2,2-crypt)][Fe(η(3)-C(8)H(8))(CO)(3)]。这两种物质都通过 EPR 和 IR 光谱以及电喷雾质谱进一步得到了表征。[Ge(8)Fe(CO)(3)]阴离子代表了一种前所未有的功能化锗 Zintl 阴离子，其中九个原子的前体簇失去了一个顶点，被一个过渡金属部分取代。