二十面体锌蒂簇的烷基化：[R-Ge9-Ge9-R]4-（R = 叔丁基、仲丁基、正丁基、叔戊基）的合成及 [叔丁基-Ge9-Ge9-叔丁基]4-的结构

Alkylation of Deltahedral Zintl clusters: synthesis of [R-Ge9-Ge9-R]4- (R = tBu, sBu, nBu, tAm and structure of [tBu-Ge9-Ge9-tBu]4-.

作者信息

Hull Michael W, Ugrinov Angel, Petrov Ivaylo, Sevov Slavi C

机构信息

Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.

出版信息

Inorg Chem. 2007 Apr 2;46(7):2704-8. doi: 10.1021/ic0623314. Epub 2007 Feb 21.

DOI:10.1021/ic0623314

PMID:17311378

Abstract

Reactions of nine-atom deltahedral clusters (Zintl ions) of germanium, Ge9n- (n = 2, 3, 4), with alkyl chlorides, RCl (R = tBu, nBu, sBu, tAm), yielded the corresponding dialkylated dimers of Ge9 clusters [R-Ge9-Ge9-R]4-. The tBu derivative with [K(2,2,2-crypt)]+ countercations was characterized in the solid state by single-crystal X-ray diffraction as [K(2,2,2-crypt)]4[tBu-Ge9-Ge9-tBu].7en (monoclinic, C2/c, a = 35.0914(10) A, b = 24.8161(6) A, and c = 16.8782(5) A, beta = 94.0136(17) degrees , V = 14662.0(7) A3, and Z = 4) and in solution by 1H and 13C NMR. All species were also characterized in solution by electrospray mass spectrometry in the negative-ion mode. These are the first main group deltahedral clusters functionalized with purely organic substituents.

摘要

锗的九原子二十面体簇（津特耳离子）Ge9n-（n = 2, 3, 4）与烷基氯RCl（R = tBu、nBu、sBu、tAm）反应，生成了相应的Ge9簇的二烷基化二聚体[R-Ge9-Ge9-R]4-。具有[K(2,2,2-穴醚)]+抗衡阳离子的叔丁基衍生物通过单晶X射线衍射在固态下表征为[K(2,2,2-穴醚)]4[tBu-Ge9-Ge9-tBu].7en（单斜晶系，C2/c，a = 35.0914(10) Å，b = 24.8161(6) Å，c = 16.8782(5) Å，β = 94.0136(17)°，V = 14662.0(7) Å3，Z = 4），并通过1H和13C NMR在溶液中表征。所有物种还通过负离子模式的电喷雾质谱在溶液中进行了表征。这些是首批用纯有机取代基官能化的主族二十面体簇。