Employing density functional theory and in
collaboration with Prof. Klingebiel's experimental
group, we reveal unknown reaction mechanisms in inorganic chemistry, in
particular in silicon , nitrogen and fluorine
chemistry. The focus is on intramolecular
rearrangements proceeding over structurally interesting transition states and
involving several reaction intermediates. Among many others, the reactions
include silylhydrazines, silylhydroxylamines and aminosiloxanes.
First
trichloroaluminum adducts of silyliminoborenes,
H. Ott, C. Matthes, S. Schmatz, U. Klingebiel and D. Stalke,
Z. Naturforsch. B 63, XXXX (2008).
From
lithium ketazides to isomeric silylketazine-rings
– Imine-enamine tautomerism,
N. Armbruster, M. Görth, U. Klingebiel and S. Schmatz,
J. Organomet. Chem. 693, 197 (2008).
Intramolecular rearrangement of organosilyl
groups in silylamines: A joint
experimental-theoretical study,
C. Matthes,
M. Noltemeyer, U. Klingebiel
and S. Schmatz,
Organometallics 26,
838 (2007).
Cyclization of di(tert-butyl-methyl)ketazine to
1,2-diaza-3-bora- and 1,2-diaza-3-sila-cyclopent-5-enes,
F. Armbruster,
N. Armbruster, U. Klingebiel,
M. Noltemeyer and S. Schmatz,
Z. Naturforsch. 61b,
1261 (2006).
Intermolecular
interconversions in cyclosilazane
chemistry: A joint experimental-theoretical study,
U. Klingebiel,
N. Helmold and S. Schmatz,
Adv. Organomet. Chem. 54,
1 (2006).
Rearrangement
of organosilyl groups between oxygen and nitrogen in aminosiloxanes, Part II,
S. Kliem,
U. Klingebiel and S. Schmatz,
J. Organomet. Chem. 690,
1100 (2005).
(Fluorosilyl)ethylenediamines and
fluorosilyl-1,3-diaza-2-silacyclopentanes,
B. Fredelake,
C. Ebker, U. Klingebiel, M.
Noltemeyer and S. Schmatz,
J. Fluor. Chem.
125, 1007 (2004).
Unusual
isomerization reactions in
1,3-diaza-2-silacyclopentanes,
S. Schmatz,
B. Fredelake, M. Jendras
and U. Klingebiel,
Organometallics 23, 1180 (2004).
Mono-
and bis(hydroxylamino)silanes - synthesis, isomerisation
and quantum chemical calculations,
C. Ebker,
S. Schmatz, F. Diedrich and
U. Klingebiel,
Silicon
Chem. 2, 117 (2003).
Isomeric
cyclosilazanes and their application as precursors
for silicon-based ceramics,
N. Helmold,
V. Liebau, U. Klingebiel
and S. Schmatz,
in: N. Auner and J. Weis (Eds.), Organosilicon Chemistry V:
From Molecules to Materials, Weinheim, Wiley-VCH, pp.
261 (2003).
Silylhydroxylamines - Synthesis, isomerisation
and quantum chemical results,
C. Ebker,
F. Diedrich, S. Schmatz and
U. Klingebiel,
in: N. Auner and J. Weis (Eds.), Organosilicon Chemistry V :
From Molecules to Materials, Weinheim, Wiley-VCH, pp.
246 (2003).
Cyclic
silylhydrazines -Synthesis, isomerisations
and quantum chemical calculations,
U. Klingebiel
and S. Schmatz,
in: N. Auner and J. Weis (Eds.), Organosilicon Chemistry V : From
Molecules to Materials, Weinheim, Wiley-VCH, pp. 233 (2003).
Stable Bis(hydroxylamino)silanes - Building
blocks for isomeric bis(silylhydroxylamino)silanes,
C. Ebker, T. Labahn, F. Diedrich, U. Klingebiel, M. Noltemeyer and S. Schmatz,
Organometallics
22, 2594 (2003).
Intramolecular rearrangement of organosilyl
groups between oxygen and nitrogen in aminosiloxanes:
A joint experimental-theoretical study,
J. Organomet. Chem. 686, 16
(2003) (Special Edition 'What's New in Silicon Chemistry?',
Eds. G. Bertrand and R. Corriu).
Aminosilanolates as precursors of four- and eight-membered (SiNSiO)-rings,
C. Reiche,
S. Kliem, U. Klingebiel, M.
Noltemeyer, C. Voit, R. Herbst-Irmer and S. Schmatz,
J. Organomet. Chem. 667,
24 (2003).
Structure
and rearrangement reactions of bis(organylsilyl)organylstannylhydroxylamines:
A joint theoretical / experimental study,
S. Schmatz,
C. Ebker, T. Labahn, H.
Stoll and U. Klingebiel,
Organometallics 22, 490 (2003).
Thermal
isomerisation of tris(silyl)hydroxylamines to silyldisiloxanes - Experimental and quantum chemical
results,
S. Schmatz,
F. Diedrich, C. Ebker and
U. Klingebiel,
Eur. J. Inorg. Chem. 2002,
876 (2002).
Unimolecular rearrangement reactions in silylpyrazolones -
A theoretical approach,
S. Schmatz,
Organometallics 21, 864 (2002).
Silylhydrazines and dimeric
N,N'-Dilithium-N,N'-bis(silyl)hydrazides - Syntheses, Reactions, Isomerisations
-,
E. Gellermann,
U. Klingebiel, T. Pape, F. Dall'Antonia, T.R. Schneider and S. Schmatz,
Z. Anorg. Allg. Chem. 2001, 2581 (2001).
Cyclisation and isomerisation
mechanisms in silylhydrazine chemistry,
U. Klingebiel,
S. Schmatz, E. Gellermann,
C. Drost and M. Noltemeyer,
Monatshefte fur Chemie (Chemical
Monthly) 132 , 1105 (2001).
Formation of (SiN2SiC)-five-membered rings by intramolecular
insertion of Si-N: A quantum chemical study,
J. Phys. Chem. A 105 , 3875
(2001).
Silyl group insertion into the N-N bond: Experimental and quantum chemical
results,
E. Gellermann, U. Klingebiel, M. Noltemeyer and S. Schmatz,
J. Am. Chem. Soc. 123 , 378 (2001).