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@ARTICLE{Grabowsky:92552,
author = {Grabowsky, S. and Hesse, M. F. and Paulmann, C. and Luger,
P. and Beckmann, J. and DESY},
title = {{H}ow to {M}ake the {I}onic {S}i-{O} {B}ond {M}ore
{C}ovalent and the {S}i-{O}-{S}i {L}inkage a {B}etter
{A}cceptor for {H}ydrogen {B}onding.},
journal = {Inorganic chemistry},
volume = {48},
issn = {0020-1669},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PHPPUBDB-11692},
pages = {4384-4393},
year = {2009},
note = {(c) American Chemical Society; Post referee fulltext in
progress 2; Embargo 12 months from publication},
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.},
keywords = {Hydrogen Bonding / Ions / Models, Molecular / Molecular
Structure / Oxides: chemistry / Silicon Compounds: chemistry
/ Siloxanes: chemistry / X-Ray Diffraction / Ions (NLM
Chemicals) / Oxides (NLM Chemicals) / Silicon Compounds (NLM
Chemicals) / Siloxanes (NLM Chemicals) / silicon monoxide
(NLM Chemicals)},
cin = {HASYLAB(-2012)},
ddc = {540},
cid = {$I:(DE-H253)HASYLAB_-2012_-20130307$},
pnm = {DORIS Beamline F1 (POF1-550)},
pid = {G:(DE-H253)POF1-F1-20130405},
experiment = {EXP:(DE-H253)D-F1-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:19379009},
UT = {WOS:000266046300014},
doi = {10.1021/ic900074r},
url = {https://bib-pubdb1.desy.de/record/92552},
}