TY  - JOUR
AU  - Grabowsky, S.
AU  - Hesse, M. F.
AU  - Paulmann, C.
AU  - Luger, P.
AU  - Beckmann, J.
AU  - DESY
TI  - How to Make the Ionic Si-O Bond More Covalent and the Si-O-Si Linkage a Better Acceptor for Hydrogen Bonding.
JO  - Inorganic chemistry
VL  - 48
SN  - 0020-1669
CY  - Washington, DC
PB  - American Chemical Society
M1  - PHPPUBDB-11692
SP  - 4384-4393
PY  - 2009
N1  - (c) American Chemical Society; Post referee fulltext in progress 2; Embargo 12 months from publication
AB  - 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.
KW  - Hydrogen Bonding
KW  - Ions
KW  - Models, Molecular
KW  - Molecular Structure
KW  - Oxides: chemistry
KW  - Silicon Compounds: chemistry
KW  - Siloxanes: chemistry
KW  - X-Ray Diffraction
KW  - Ions (NLM Chemicals)
KW  - Oxides (NLM Chemicals)
KW  - Silicon Compounds (NLM Chemicals)
KW  - Siloxanes (NLM Chemicals)
KW  - silicon monoxide (NLM Chemicals)
LB  - PUB:(DE-HGF)16
C6  - pmid:19379009
UR  - <Go to ISI:>//WOS:000266046300014
DO  - DOI:10.1021/ic900074r
UR  - https://bib-pubdb1.desy.de/record/92552
ER  -