Synthesis, characterization and reactions of the Vinylbis(trimethylsilyl)silyl anion

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Journal of Organometallic Chemistry Pub Date : 2025-02-24 DOI:10.1016/j.jorganchem.2025.123589

Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester

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引用次数: 0

Abstract

The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium tert-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by ¹H, ¹³C and ²⁹Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph₃SiCl, Ph₂MeSiCl, PhCH₂Cl and BrCH₂CH₂Br have been studied and the crystal structure of the product from reaction with Ph₃SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.

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来源期刊

Journal of Organometallic Chemistry 化学-无机化学与核化学

CiteScore

4.40

自引率

8.70%

发文量

221

审稿时长

36 days

期刊介绍： The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds. Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome. The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.