TY - JOUR

T1 - Synthesis and Characterization of Alkali Metal Hypersilyl Borates

AU - Lainer, Thomas

AU - Walkner, Christoph

AU - Tasch, Nina M.

AU - Fischer, Roland C.

AU - Torvisco, Ana

AU - Stueger, Harald

AU - Haas, Michael

N1 - Publisher Copyright: © 2024 The Author(s). Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH.

PY - 2024/7/22

Y1 - 2024/7/22

N2 - This study focuses on the synthesis of H- and MeO- functionalized alkali metal hypersilyl borates. Consequently, two distinct silanides were used as polysilane frameworks for our chemical manipulations. Tris(silyl)silanide (1) and tris(trimethoxysilyl)silanide (2) react in the same manner with the BH3 ⋅ SMe2 complex to obtain two new alkali metal hypersilyl borates [(R3Si)3SiBH3M (M=alkali metal; R=H, (3), R=MeO, (4 a–c))] in good to excellent yields. NMR spectroscopy for all compounds and single-crystal X-ray crystallography for 3 and 4 a, b enabled a clear structural characterization. Single crystal X-ray analysis of 3 showed a dimeric structure, where two THF-molecules and three hydrides from the BH3-group contribute to the coordination sphere of the lithium atom. Interestingly, crystals suitable for X-ray analysis of 4 a and 4 b showed a solvent-free cluster formation, due to the coordination of the MeO groups. Both species form coordination polymers with different coordination modes depending on the nature of the alkali metal. Attempted hydride abstraction reactions of 3 and 4 with various reagents under the formation of the free boranes proceeded unselectively.

AB - This study focuses on the synthesis of H- and MeO- functionalized alkali metal hypersilyl borates. Consequently, two distinct silanides were used as polysilane frameworks for our chemical manipulations. Tris(silyl)silanide (1) and tris(trimethoxysilyl)silanide (2) react in the same manner with the BH3 ⋅ SMe2 complex to obtain two new alkali metal hypersilyl borates [(R3Si)3SiBH3M (M=alkali metal; R=H, (3), R=MeO, (4 a–c))] in good to excellent yields. NMR spectroscopy for all compounds and single-crystal X-ray crystallography for 3 and 4 a, b enabled a clear structural characterization. Single crystal X-ray analysis of 3 showed a dimeric structure, where two THF-molecules and three hydrides from the BH3-group contribute to the coordination sphere of the lithium atom. Interestingly, crystals suitable for X-ray analysis of 4 a and 4 b showed a solvent-free cluster formation, due to the coordination of the MeO groups. Both species form coordination polymers with different coordination modes depending on the nature of the alkali metal. Attempted hydride abstraction reactions of 3 and 4 with various reagents under the formation of the free boranes proceeded unselectively.

KW - boron

KW - hydrosilanes

KW - methoxysilanes

KW - silicon

KW - silylborate

UR - http://www.scopus.com/inward/record.url?scp=85199087940&partnerID=8YFLogxK

U2 - 10.1002/zaac.202400054

DO - 10.1002/zaac.202400054

M3 - Article

AN - SCOPUS:85199087940

VL - 650.2024

JO - Zeitschrift für anorganische und allgemeine Chemie

JF - Zeitschrift für anorganische und allgemeine Chemie

SN - 0044-2313

IS - 15

M1 - e202400054

ER -