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ORGANOLITHIUM REACTIVITY AND LIGAND DESIGN IN BIS(AMINO)SILANE SYSTEMS: SYNTHESIS, STRUCTURAL ELUCIDATION, AND ACTIVATION OF POLAR SUBSTRATES
Rok: 2025
Druh publikace: ostatní - přednáška nebo poster
Strana od-do: nestránkováno
Tituly:
Jazyk Název Abstrakt Klíčová slova
eng ORGANOLITHIUM REACTIVITY AND LIGAND DESIGN IN BIS(AMINO)SILANE SYSTEMS: SYNTHESIS, STRUCTURAL ELUCIDATION, AND ACTIVATION OF POLAR SUBSTRATES Sterically hindered lithium bis(amino)silanes were synthesized and structurally characterized to evaluate their potential as highly reactive polar organometallic intermediates. Employing stepwise lithiation with n-BuLi under inert conditions, mono- and bis-lithiated species were obtained and analyzed via multinuclear NMR (¹H, ¹³C, ⁷Li) and single-crystal X-ray diffraction (SC-XRD) 1. The introduction of bulky aryl substituents on nitrogen significantly influenced coordination geometries and aggregation states 2. Reactions with ethers such as diethyl ether demonstrated unprecedented C–O bond cleavage, yielding well-defined lithium alkoxide clusters 3. In addition, reactivity with N,N′-diisopropylcarbodiimide afforded lithium amidosilylguanidinates, providing new insights into nucleophilic addition pathways involving polar metal-ligand frameworks. These findings open new perspectives on ligand behavior in main-group element chemistry and the design of controlled synthetic routes to low-valent compounds. The results represent a step forward in the development of reactive, low-coordinate main-group complexes for small molecule activation and novel bond-forming processes. ORGANOLITHIUM; REACTIVITY; LIGAND; DESIGN; BISAMINOSILANE; SYSTEMS; SYNTHESIS; STRUCTURAL; ELUCIDATION; AND; ACTIVATION; POLAR; SUBSTRATES