Tin-Based Organo-Zintl Ions: Alkylation and Alkenylation of Sn94−
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- 作者：Donald J. Chapman ; Slavi C. Sevov
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：July 7, 2008
- 年：2008
- 卷：47
- 期：13
- 页码：6009 - 6013
- 全文大小：267K
- 年卷期：v.47,no.13(July 7, 2008)
- ISSN：1520-510X
文摘
Reactions of nine-atom deltahedral clusters (Zintl ions) of tin, Sn94−, with alkyl chlorides, RCl (R = tBu, nBu, sBu), and alkynes (Me3Si−C≡C−SiMe3, Ph−C≡CH) yielded the corresponding alkylated and alkenylated clusters [Sn9−R]3−. The triple bonds of the alkynes are hydrogenated to double bonds in the process. These are the first tin-based organo-Zintl ions, that is Zintl ions of tin that were subsequently functionalized with organic groups. They are analogous to the recently reported germanium-based derivatives. The tBu-, vinyl-, and styrene-functionalized clusters [Sn9−tBu]3−, [Sn9−CH=CH2]3−, and [Sn9−CH=CH−Ph]3−, respectively, were structurally characterized in the solid state with [K(2,2,2-crypt)]+ countercations and in solution by electrospray mass spectrometry. Crystal data: [K(2,2,2-crypt)]3[Sn9-tBu]·2py, triclinic, P1, a = 14.4259(3), b = 16.2725(4), and c = 22.5593(5) Å, α = 86.092(1), β = 78.952(1), and γ = 65.114(1)°, V = 4714.48(7) Å3, Z = 2; [K(2,2,2-crypt)]3[Sn9−CH=CH2]·2py, triclinic, P-1, a = 15.6988(3), b = 17.4195(4), and c = 17.4432(4) Å, α = 86.299(1), β = 81.566(1), and γ = 85.349(1) °, V = 4696.27(18) Å3, Z = 2; [K(2,2,2-crypt)]3[Sn9−CH=CH-Ph]·tol·0.75py, monoclinic, C2/c, a = 38.5883(9), b = 23.3893(5), and c = 25.0192(5) Å, β = 120.269(1) °, V = 19502.6(7) Å3, Z = 8.