Bis[N,N鈥?diisopropylbenzamidinato(鈭?]silicon(II): Cycloaddition Reactions with Organic 1,3-Dienes and 1,2-Diketones

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• 作者：Nadine Laskowski ; Konstantin Junold ; Claudia Kupper ; Johannes A. Baus ; Christian Burschka ; Reinhold Tacke
• 刊名：Organometallics
• 出版年：2014
• 出版时间：November 10, 2014
• 年：2014
• 卷：33
• 期：21
• 页码：6141-6148
• 全文大小：377K
• ISSN：1520-6041

文摘

Reaction of the donor-stabilized silylene 1 (which is three-coordinate in the solid state and four-coordinate in solution) with organic 1,3-dienes (2,3-dimethyl-1,3-butadiene, 1,3-butadiene, (E,E)-1,4-diphenyl-1,3-butadiene, 2,3-dibenzyl-1,3-butadiene, 1,3-cyclohexadiene, or cyclooctatetraene) and 1,2-diketones (3,5-di-tert-butyl-1,2-benzoquinone or 1,2-diphenylethane-1,2-dione) leads to the formation of the respective cycloaddition products 2鈥?b>9. Compounds 2鈥?b>9 were characterized by crystal structure analyses (7 was studied as the hemi solvate 7路0.5n-C₆H₁₄) and NMR spectroscopic studies in the solid state and in solution. As the amidinato ligands can switch between a monodentate and bidentate coordination mode, for some of the cycloaddition products studied, the silicon coordination number in the solid state and in solution is different. For example, compound 4 is four- (4a) and six-coordinate (4b) in the solid state (isolated as a 1:1 cocrystallizate of 4a and 4b) and five-coordinate in solution. As demonstrated for the methanolysis of 2 (formation of 10; proof of principle), compounds 2鈥?b>7 with their reactive Si鈥揘 bonds are starting materials for the synthesis of promising mono- and bicyclic organosilicon compounds.