title: Introducing a Hydrogen-Bond Donor into a Weakly Nucleophilic Brønsted Base: Alkali Metal Hexamethyldisilazides (MHMDS, M=Li, Na, K, Rb and Cs) with Ammonia.
abstract: Alkali metal 1,1,1,3,3,3-hexamethyldisilazide (MHMDSs) are one of the most utilised weakly nucleophilic Brønsted bases in synthetic chemistry and especially in natural product synthesis. Like lithium organics, they aggregate depending on the employed donor solvents. Thus, they show different reactivity and selectivity as a function of their aggregation and solvation state. To date, monomeric LiHMDS with monodentate donor bases was only characterised in solution. Since the first preparation of LiHMDS in 1959 by Wannagat and Niederprüm, all efforts to crystallise monomeric LiHMDS in the absence of chelating ligands failed. Herein, we present ammonia adducts of LiHMDS, NaHMDS, KHMDS, RbHMDS and CsHMDS with unprecedented aggregation motifs: 1) The hitherto missing monomeric key compound in the LiHMDS aggregation architectures. Monomeric crystal structures of trisolvated LiHMDS (1) and NaHMDS (2), showing unique intermolecular hydrogen bonds, 2) the unprecedented tetrasolvated KHMDS (3) and RbHMDS (4) dimers and 3) the disolvated CsHMDS (5) dimer with very close intermolecular Si-CH3 ⋅⋅⋅Cs s-block "agostic" interactions have been prepared and characterised by single-crystal X-ray structure analysis.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.
authors.forename: Roman
authors.initials: R
authors.lastname: Neufeld
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.
authors.forename: Reent
authors.initials: R
authors.lastname: Michel
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.
authors.forename: Regine
authors.initials: R
authors.lastname: Herbst-Irmer
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.
authors.forename: Ralf
authors.initials: R
authors.lastname: Schöne
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany. dstalke@chemie.uni-goettingen.de.
authors.forename: Dietmar
authors.initials: D
authors.lastname: Stalke
keywords: X-ray diffraction; amides; hydrogen bonds; reactive intermediates; solvent effects