1,4-diazadiene imido complexes of group V and VI elements and their application in chemical vapour deposition of TaN films [Elektronische Ressource] / vorgelegt von Alexei A. Merkoulov

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1,4–Diazadiene Imido Complexes of Group V and VI Elements and Their Application in Chemical Vapour Deposition of TaN Films Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften (Dr. rer. nat.) dem Fachbereich Chemie der Philipps-Universität Marburg vorgelegt von Alexei A. Merkoulov aus Himki (Russland) Marburg / Lahn 2005 Die vorliegende Dissertation entstand in der Zeit von Oktober 2001 bis März 2005 unter Leitung von Herrn Prof. Dr. J. Sundermeyer am Fachbereich Chemie der Philipps-Universität Marburg. Vom Fachbereich Chemie der Philipps-Universität Marburg als Dissertation angenommen am 25.10.2005 Erstgutachter: Herr Prof. Dr. J. Sundermeyer Zweitgutachter: Herr Prof. Dr. M. Bröring Tag der Disputation: 27.10.2005 Science does not believe in marvels, but always looks forward to marvellous coincidences Wilhelm Schwebel To my parents Prologue This dissertation is written in a manuscript style; each chapter can be read independently, yet they all interact. Each chapter contains a separate summary, introduction, results and discussion part, conclusion, experimental section and literature references.

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1,4–Diazadiene Imido Complexes
of Group V and VI Elements
and
Their Application in Chemical Vapour
Deposition of TaN Films


Dissertation
zur
Erlangung des Doktorgrades
der Naturwissenschaften
(Dr. rer. nat.)

dem
Fachbereich Chemie
der Philipps-Universität Marburg
vorgelegt von

Alexei A. Merkoulov
aus
Himki (Russland)
Marburg / Lahn 2005
























Die vorliegende Dissertation entstand in der Zeit von Oktober 2001 bis März 2005 unter Leitung
von Herrn Prof. Dr. J. Sundermeyer am Fachbereich Chemie der Philipps-Universität Marburg.


Vom Fachbereich Chemie der Philipps-Universität Marburg als Dissertation angenommen am
25.10.2005


Erstgutachter: Herr Prof. Dr. J. Sundermeyer
Zweitgutachter: Herr Prof. Dr. M. Bröring


Tag der Disputation: 27.10.2005





Science does not believe in marvels,
but always looks forward to marvellous coincidences

Wilhelm Schwebel
























To my parents


Prologue


This dissertation is written in a manuscript style; each chapter can be read
independently, yet they all interact. Each chapter contains a separate summary, introduction,
results and discussion part, conclusion, experimental section and literature references. It should
be noted that the repetition of certain facts and the citation of literature from chapter to chapter is
useful under these circumstances and cannot be avoided in order to retain the independence and
clarity of each chapter.


In the „General Introduction“ an overview of complexes with early transition metals
supported by 1,4–diazadiene ligands is given, whereas more details about specific topics are
discussed in the introduction of the relevant chapter.
Finally, an overall summary, which combines the separate chapters and their results in
common context, is provided.


















Parts of this dissertation have been published


Publications

Alexei Merkoulov, Simone Schmidt, Klaus Harms, and Jörg Sundermeyer, “Mononuclear
Imido Amido Complexes via Exhaustive Ammonolysis of Niobium and Tantalum
Pentachloride with tert-Butyl Amine”, Z. Anorg. Allg. Chem. 2005, 631, 1810-1812

Alexei Merkoulov, Klaus Harms and Jörg Sundermeyer, “Synthesis and Investigations on the
Crystal Structure of a Dinuclear Diazadiene Molybdenum Oximid with an Unique
N Mo(µ-O) MoN Core”, Eur. J. Inorg. Chem., accepted, in press 3 2 3

Alexei Merkoulov, Klaus Harms, and Jörg Sundermeyer, “Synthesis and Structural
Characterisation of 1,4-Diazadiene Imido Tungsten Complexes”, Z. Anorg. Allg. Chem.,
accepted, in press


Patents

“Tantal- und Niob-Verbindungen und ihre Verwendung für die Chemical Vapour
Deposition (CVD)”, Inventors: J. Sundermeyer, A. Merkoulov, W. Stolz, K. Volz, M. Pokoj, T.
Ochs, Assignee: H.C. Starck GmbH, 2005


Presentations

“1,4-Diazadiene Imido Complexes – A Fruitful Liaison of π-Acidic and π-Basic Ligands”,
8th Seminar of PhD Students on Organometallic Chemistry, 2003, Hruba Scala, Czech Republic

“1,4-Diazadien-Imido-Komplexe der Metalle der Gruppe 5 und 6”, Anorganisches
Kolloqium des FB Chemie, 2004, Philipps Universität Marburg


Explanations

Abbreviations
acac Acetylacetonate
allAllyl, C H3 5
Ar Aromaticsubstituent
Ar 2,3,4,5,6-Pentafluorophenyl F
B Base
BzBenzyl
Cp Cyclopentadienyl
CyCyclohexyl
R,R’–DAD Substituted 1,4-diazadiene (R at nitrogen and R’ at carbon atoms)
DAD, dad 1,4-Diazadiene, if not specified 1,4-di-tert-butyl-1,4-diaza-1,3-diene
Dip 2,6-Di-iso-propylphenyl
DME1,2-Dimethoxyethane
DMSO Dimethylsulfoxide
DNMRDynamic NMR
EI Electron Ionisation
IndIndenyl
iPr iso-Propyl
L Any ligand
MeMethyl
Mes Mesityl (2,4,6-trimethylphenyl)
MMAMethylmethacrylate
MS Mass Spectroscopy
NMR Nuclear Magnetic Resonance
Ph Phenyl
PyPyridine
tBu tert-Butyl
THF Tetrahydrofurane

Numbers
Compounds are labelled with full-size, bold numbers, e.g. 3.
[8]Numbers in square brackets indicate a reference (e.g. example [4] or elevated example ).
Acknowledgments


First of all, I would like to thank my Ph.D. supervisor, Prof. Dr. Jörg Sundermeyer, for
the interesting research topics and his readiness for fruitful advice and discussions throughout
this work.

My special thanks for loyalty and patience go to the magician in crystallography,
Dr. Klaus Harms, who has solved all crystal structures discussed here.

The members of the NMR division, Dr. Xiulan Xie, Gert Häde and Alphonse
Mbonimana, are gratefully acknowledged for their inappreciable help in first-hand acquaintance
with NMR technique.

All members of the research group are to be mentioned for providing a nice atmosphere
and “one team” feeling. Especially I would like to thank Udo Garrelts for his help in my first
steps in Germany, Daniel Gaess and Thomas Linder for the correction of grammar and contents.

Also the work of the mechanical and glassware sections has to be thankfully
remembered for the outstanding performance of non-standard apparatuses.

My grateful thanks are addressed to Prof. Dr. Wolfgang Stolz and to the members of his
workgroup, especially to Michael Pokoj and Dr. Kerstin Volz, for everything that concerns
Chemical Vapour Deposition.

Financial support from the Deutsche Forschungsgemeinschaft (DFG) and H.C. Starck
GmbH is gratefully acknowledged.

Finally, I would like to thank Ekaterina Gauchenova for her endless patience and
invaluable support.





Table of content


Zusammenfassung.................................................................................................1

General Introduction ............................................................................................9
References ........................................................................................................................12

Chapter I. Preparation of New Dimethoxymethane (DME) and Neutral
1,4-Diazadiene (DAD) Imido Complexes of Niobium and Tantalum ............15
Introduction.....................................................................................................................15
Results and discussion ....................................................................................................17
Preparative studies...............................................................................................................17
Spectroscopic studies...........................................................................................................19
X-ray studies........................................................................................................................20
Conclusion........................................................................................................................21
Experimental Part...........................................................................................................21
References...25

Chapter II. Synthesis and Structural Characterisation of 1,4-Diazadiene
Imido Tungsten Complexes................................................................................26
Abstract............................................................................................................................26
Introduction.....................................................................................................................26
Results and discussion ....................................................................................................27
Conclusion........................................................................................................................30
Experimental Part...........................................................................................................31
References...32

Chapter III. Synthesis and Investigations on the Crystal Structure of a
Dinuclear Diazadiene Molybdenum Oxo-imido with an Unique
N Mo(µ-O) MoN Core.......................................................................................34 3 2 3
Summary..........................................................................................................................34
Introduction.....................................................................................................................34
Results and discussion ....................................................................................................35
Experimental Part...........................................................................................................40
References ........................................................................................................................42
Chapter IV. Dynamic Effects in 1,4-Diaza-1,3-diene Complexes
[M(NR) (DAD)] of Chromium Triad Metals....................................................44 2
Abstract............................................................................................................................44
Introduction.....................................................................................................................44
Results and discussion ....................................................................................................45
Preparative studies...................................................................................................45
2–Activation parameters of the DAD inversion .......................................................62
Conclusion........................................................................................................................65
Experimental Part...........................................................................................................66
References...69

Chapter V. Dynamic Processes in the New DAD Niobium and Tantalum
Complexes of the Types [(DAD)M(NR)(X)(L)] and [(DAD)M(NR)(µ-Cl)] .74 2
Introduction.....................................................................................................................74
Results and discussion ....................................................................................................76
Synthetic studies ......................................................................................................76
MS studies ...............................................................................................................96
IR studies .................................................................................................................97
NMR studies ............................................................................................................97
DNMR studies .........................................................................................................97
Conclusion......................................................................................................................111
Experimental Part111
References.118

Chapter VI. Chemical Reactivity of DAD Niobium and Tantalum
tComplexes of the Type [(DAD)M(N Bu)(Cl)(L)]............................................122
Introduction...................................................................................................................122
Results and discussion ..................................................................................................123
Synthetic studies ....................................................................................................123
MS studies .............................................................................................................145
IR studies ...............................................................................................................146
NMR studies ..........................................................................................................146
Conclusion......................................................................................................................146
Experimental Part.........................................................................................................147
References.155