Journal Article

PHPPUBDB-11692

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png How to Make the Ionic Si-O Bond More Covalent and the Si-O-Si Linkage a Better Acceptor for Hydrogen Bonding.

Grabowsky, S. ; Hesse, M. F. ; Paulmann, C. ; Luger, P. ; Beckmann, J. ; DESY

2009
American Chemical Society Washington, DC

This record in other databases:      

Please use a persistent id in citations: doi:10.1021/ic900074r

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.

Keyword(s): Hydrogen Bonding (MeSH) ; Ions (MeSH) ; Models, Molecular (MeSH) ; Molecular Structure (MeSH) ; Oxides: chemistry (MeSH) ; Silicon Compounds: chemistry (MeSH) ; Siloxanes: chemistry (MeSH) ; X-Ray Diffraction (MeSH) ; Ions ; Oxides ; Silicon Compounds ; Siloxanes ; silicon monoxide

Note: (c) American Chemical Society; Post referee fulltext in progress 2; Embargo 12 months from publication

---

Contributing Institute(s):

1. Experiments with synchrotron radiation (HASYLAB(-2012))

Research Program(s):

1. DORIS Beamline F1 (POF1-550) (POF1-550)

Experiment(s):

1. DORIS Beamline F1 (DORIS III)

Appears in the scientific report 2009
Notes: (c) American Chemical Society. No copyright permission for full text.

---

Database coverage:
; JCR ; No Author Disambiguation ; No Authors Fulltext ; Thomson Reuters Master Journal List ; Web of Science Core Collection

---