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The Reaction of Polycyclic Alkoxysilylamides of Li, Na, and K with Organic Lewis Bases

Independently of the ligand at the nitrogen atom (tert-butyl or trimethylsilyl) the polycyclic and dimeric lithium (alkoxysilyl)-tert-butylamide 1 or lithium (alkoxysilyl)silylamide 2 react with bases like pyridine, tetrahydrofuran, or dioxane to form the acid-base adducts 1a, 1b, 1c, and 2a of similar structure.An X-ray structure analysis of 1b confirms the base tetrahydrofuran being coordinated by the oxygen to one of the lithium atoms while the other is surrounded by oxygen and nitrogen atoms of the siloxyamide ligand.The two metal atoms have different coordination numbers (3 versus 4), the shorter distances are found at the one with less neighbours.Even an excess of the base does not lead to complexes in which the two metal atoms within the molecule have equal degree of saturation or have an equal environment.Nevertheless this situation can be reached with the corresponding sodium compound 3, which forms 3a by contact with pyridine.In this product the two sodium atoms have an identical coordination sphere being bound to three nitrogen and one oxygen atom.A compound with different sodium atoms is formed when 3 is treated with alpha,alpha’-bipyridine.This astonishing unsymmetry in the coordination of the two metal atoms is not realized in the corresponding potassium compound 4a, formed from 4 and alpha,alpha’-bipyridine (equally coordinated potassium atoms).The existence of acid-base adducts of 3 and 4 with phenanthroline and different crown ethers has been proven. – Key Words: Lewis acid-base adducts / Alkali metal amides / Chelated metals

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Chiral Catalysts,
Chiral catalysts – SlideShare