第 14 族杂原子二十面体 Zintl 离子及其烯基化。

Heteroatomic deltahedral zintl ions of group 14 and their alkenylation.

机构信息

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

出版信息

Inorg Chem. 2010 Jan 18;49(2):721-9. doi: 10.1021/ic9019487.

DOI:10.1021/ic9019487

PMID:20000832

Abstract

Reported is the synthesis of Ge(9-x)Sn(x) heteroatomic deltahedral Zintl ions and their alkenylation by reactions with alkynes. The nine-atom clusters are made either by extraction from mixed Ge/Sn precursors with nominal composition K(4)Ge(9-x)Sn(x) or by dissolution of mixtures of the corresponding binary precursors K(4)Ge(9) and K(4)Sn(9) in solvents with high dielectric constants such as DMF, DMSO, and acetonitrile. Reactions of the heteroatomic clusters with alkynes such as Me(3)SiC[triple bond]CSiMe(3), HC[triple bond]CCpr (Cpr = cyclopropyl), and HC[triple bond]CPh in ethylenediamine resulted in the following structurally characterized compounds with alkenylated heteroatomic clusters: K-(2,2,2-crypt)[GeSn(8)-CH=CH(2)].en.tol (1), triclinic, P1, a = 13.9220(3) A, b = 14.9788(3) A, and c = 21.5892(5) A, alpha = 94.2580(10) degrees , beta = 98.5210(10) degrees , and gamma = 98.4890(10) degrees , V = 4382.31(16) A(3), Z = 2; K-(2,2,2-crypt)Ge(2)Sn(7)(CH=CH(2))(2).en (2), monoclinic, P2(1)/c, a = 48.1883(15) A, b = 12.1551(4) A, and c = 21.4824(7) A, beta = 90.052(2) degrees , V = 12583.0(7) A(3), Z = 4; K-(2,2,2-crypt)[GeSn(8)-CH=CHCpr].en (3), monoclinic, P2(1)/c, a = 17.9132(9) A, b = 22.7967(11) A, and c = 21.6922(12) A, beta = 98.409(2) degrees , V = 8763.0(8) A(3), Z = 4; K-(2,2,2-crypt)[Ge(2)Sn(7)-CH=CHPh].2en (4), monoclinic, P2(1)/n, a = 13.2583(5) A, b = 47.0565(17) A, and c = 15.9978(6) A, beta = 111.536(2) degrees , V = 9284.1(6) A(3), Z = 4. The potassium countercations of the divinyl-substituted cluster in 2 were exchanged for tetrapropylammonium cations, and the resulting compound was also crystallized and structurally characterized: Pr(4)N Ge(2)Sn(7)(CH=CH(2))(2) (5), triclinic, P1, a = 11.6757(8) A, b = 18.8150(16) A, and c = 21.0608(17) A, alpha = 112.327(3) degrees , beta = 91.550(3) degrees , and gamma = 91.892(3) degrees , V = 4273.5(6) A(3), Z = 2. All clusters were also characterized in solution by electrospray mass spectrometry.

摘要

报道了 Ge(9-x)Sn(x) 杂原子二十面体 Zintl 离子的合成及其与炔烃的烯基化反应。这些九原子簇要么通过从具有标称组成 K(4)Ge(9-x)Sn(x) 的混合 Ge/Sn 前体中提取，要么通过在高介电常数溶剂如 DMF、DMSO 和乙腈中溶解相应的二元前体 K(4)Ge(9) 和 K(4)Sn(9) 来制备。杂原子簇与炔烃如 Me(3)SiC[三重键]CSiMe(3)、HC[三重键]CCpr (Cpr = 环丙基)和 HC[三重键]CPh 在乙二胺中的反应得到了以下结构特征的化合物，其中含有烯基化杂原子簇：[K-(2,2,2- 穴醚)]3[GeSn(8)-CH=CH(2)].en.tol (1)，三斜晶系，P1，a = 13.9220(3) A，b = 14.9788(3) A，c = 21.5892(5) A，α = 94.2580(10) 度，β = 98.5210(10) 度，γ = 98.4890(10) 度，V = 4382.31(16) A(3)，Z = 2；[K-(2,2,2- 穴醚)]4Ge(2)Sn(7)(CH=CH(2))(2).en (2)，单斜晶系，P2(1)/c，a = 48.1883(15) A，b = 12.1551(4) A，c = 21.4824(7) A，β = 90.052(2) 度，V = 12583.0(7) A(3)，Z = 4；[K-(2,2,2- 穴醚)]3[GeSn(8)-CH=CHCpr].en (3)，单斜晶系，P2(1)/c，a = 17.9132(9) A，b = 22.7967(11) A，c = 21.6922(12) A，β = 98.409(2) 度，V = 8763.0(8) A(3)，Z = 4；[K-(2,2,2- 穴醚)]3[Ge(2)Sn(7)-CH=CHPh].2en (4)，单斜晶系，P2(1)/n，a = 13.2583(5) A，b = 47.0565(17) A，c = 15.9978(6) A，β = 111.536(2) 度，V = 9284.1(6) A(3)，Z = 4。2 中二乙烯基取代簇的钾反离子被四丙基铵阳离子交换，得到的化合物也进行了结晶和结构表征：Pr(4)N Ge(2)Sn(7)(CH=CH(2))(2) (5)，三斜晶系，P1，a = 11.6757(8) A，b = 18.8150(16) A，c = 21.0608(17) A，α = 112.327(3) 度，β = 91.550(3) 度，γ = 91.892(3) 度，V = 4273.5(6) A(3)，Z = 2。所有的簇也通过电喷雾质谱在溶液中进行了表征。