title: How to make the ionic Si-O bond more covalent and the Si-O-Si linkage a better acceptor for hydrogen bonding.
abstract: Variation of a bond angle can tune the reactivity of a chemical compound. To exemplify this concept, the nature of the siloxane linkage (Si-O-Si), the most abundant chemical bond in the earth's crust, was examined using theoretical calculations on the molecular model compounds H(3)SiOSiH(3), (H(3)Si)(2)OHOH, and (H(3)Si)(2)OHOSiH(3) and high-resolution synchrotron X-ray diffraction experiments on 5-dimethylhydroxysilyl-1,3-dihydro-1,1,3,3-tetramethyl-2,1,3-benzoxadisilole (1), a molecular compound that gives rise to the formation of very rare intermolecular hydrogen bonds between the silanol groups and the siloxane linkages. For theoretical calculations and experiment, electronic descriptors were derived from a topological analysis of the electron density (ED) distribution and the electron localization function (ELF). The topological analysis of an experimentally obtained ELF is a newly developed methodology. These descriptors reveal that the Si-O bond character and the basicity of the siloxane linkage strongly depend on the Si-O-Si angle. While the ionic bond character is dominant for Si-O bonds, covalent bond contributions become more significant and the basicity increases when the Si-O-Si angle is reduced from linearity to values near the tetrahedral angle. Thus, the existence of the exceptional intermolecular hydrogen bond observed for 1 can be explained by its very small strained Si-O-Si angle that adopts nearly a tetrahedral angle.
authors.affiliation: Kristallographie, Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 36a, 14195 Berlin, Germany.
authors.forename: Simon
authors.initials: S
authors.lastname: Grabowsky
authors.forename: Maxie F
authors.initials: MF
authors.lastname: Hesse
authors.forename: Carsten
authors.initials: C
authors.lastname: Paulmann
authors.forename: Peter
authors.initials: P
authors.lastname: Luger
authors.forename: Jens
authors.initials: J
authors.lastname: Beckmann
mesh_terms: D006860:Hydrogen Bonding; D007477:Ions; D008958:Models, Molecular; D015394:Molecular Structure; D010087:Oxides / Q000737:chemistry; D017655:Silicon Compounds / Q000737:chemistry; D012833:Siloxanes / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D007477:Ions; D010087:Oxides; D017655:Silicon Compounds; D012833:Siloxanes; C116473:silicon monoxide