一种不寻常的锗（II）杯[4]芳烃配合物和首个锗（II）杯[8]芳烃配合物的合成、结构及其与九羰基二铁的反应活性

Synthesis and structures of an unusual germanium(II) calix[4]arene complex and the first germanium(II) calix[8]arene complex and their reactivity with diiron nonacarbonyl.

作者信息

Wetherby Anthony E, Goeller Lindy R, DiPasquale Antonio G, Rheingold Arnold L, Weinert Charles S

机构信息

Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078, USA.

出版信息

Inorg Chem. 2007 Sep 3;46(18):7579-86. doi: 10.1021/ic700969m. Epub 2007 Aug 11.

DOI:10.1021/ic700969m

PMID:17691771

Abstract

The protonolysis reaction of the germanium(II) amide Ge[N(SiMe3)2]2 with calix[4]arene and calix[8]arene furnishes the two germanium(II) calixarene complexes {calix[4]}Ge2 and {calix[8]}Ge4, respectively, which have been crystallographically characterized. The calix[4]arene complex contains a Ge2O2 rhombus at the center of the molecule and is one of the only four germanium(II) calix[4]arenes that have been structurally characterized. The calix[8]arene species is the first reported germanium calix[8]arene complex, and it exhibits an overall bowl-shaped structure which contains two Ge2O2 fragments. The latter complex reacts with Fe2(CO)9 to yield an octairon compound, which has also been structurally characterized and contains four GeFe2 triangles arranged around the macrocyclic ring. The germanium(II) centers are oxidized to germanium(IV) in this process, with concomitant reduction of the neutral diiron species to Fe2(CO)(8)2- anions.

摘要

锗（II）酰胺Ge[N(SiMe3)2]2与杯[4]芳烃和杯[8]芳烃的质子解反应分别生成了两种锗（II）杯芳烃配合物{杯[4]}Ge2和{杯[8]}Ge4，它们已通过晶体学表征。杯[4]芳烃配合物在分子中心含有一个Ge2O2菱形，是仅有的四个已进行结构表征的锗（II）杯[4]芳烃之一。杯[8]芳烃物种是首次报道的锗杯[8]芳烃配合物，它呈现出整体碗状结构，包含两个Ge2O2片段。后一种配合物与Fe2(CO)9反应生成一种八铁化合物，该化合物也已通过结构表征，并且包含围绕大环排列的四个GeFe2三角形。在此过程中，锗（II）中心被氧化为锗（IV），同时中性二铁物种被还原为Fe2(CO)(8)2-阴离子。