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![The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)
The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Synthesis and One-Electron Reduction of Donor-Acceptor-Stabilized SiII-EII-SiII Trimetallylenes (E = Ge, Sn, Pb)
Chaopeng Hu1, Shenglai Yao1, Christian Lorent2
1Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Berlin, Germany.
Abstract:
Herein, we report isolable donor-acceptor-stabilized SiII-EII-SiII trimetallylenes (E = Ge (2), Sn (3), Pb (4); SiII = Mes(cAAC)Si; Mes = 2,4,6-Me3C6H2; cAAC = C(CH2)(CMe2)2N-2,6-iPr2C6H3), stabilized by a cyclic alkylaminocarbene attached to the divalent Si atoms. They were synthesized through salt-metathesis reactions of the dimeric silanylidene anion (SiIIK)2 1a and EX2 precursors (X = Cl, N(SiMe3)2). Computational analyses reveal that 2-4 adopt bent donor-acceptor-stabilized SiII-EII-SiII frameworks featuring polarized Si-C(cAAC) π interactions together with delocalized Si-E π interactions involving the Lewis-acidic EII center. This donor-acceptor electronic structure results in small HOMO-LUMO gaps, giving rise to pronounced near-infrared (NIR) absorption. Remarkably, the one-electron reduction of 2 and 3 leads to the GeI- and SnI- radical anions 2•- and 3•-, respectively, thereby highlighting that this donor-acceptor motif can even stabilize heavy Group 14 elements in lower oxidation states.
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