Design of rare-earth organometallic complexes stabilized by novel cyclopentadienyl-phosphazene and modified dialkylbenzylamine ligand regimes [Elektronische Ressource] / vorgelegt von Alexander R. Petrov

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• Publié par: philipps-universitat_marburg
• Publié le: 01 janvier 2008
• Nombre de lectures: 65
• Poids de l'ouvrage: 3 Mo

Extrait

Design of Rare-Earth Organometallic Complexes Stabilized by
Novel Cyclopentadienyl-Phosphazene and Modified
Dialkylbenzylamine Ligand Regimes



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

dem
Fachbereich Chemie
der Philipps-Universität Marburg
vorgelegt von


Alexander R. Petrov
aus
Yakutsk, Russland



Marburg/Lahn
2008



Die vorliegende Dissertation entstand in der Zeit von Oktober 2002 bis August 2008 am
Fachbereich Chemie der Philipps-Universität Marburg in der Arbeitsgruppe und unter
Betreuung von Herrn Prof. Dr. Jörg Sundermeyer und Herrn Dr. Konstantin A. Rufanov
(Chemistry Department, M. V. Lomonosov State University of Moscow).



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










Erstgutachter: Herr Prof. Dr. Jörg Sundermeyer
Zweitgutachter: Herr Prof. Dr. Martin Bröring

Wissenschaftlicher Betreuer: Herr Dr. Konstantin A. Rufanov




Tag der mündlichen Prüfung am 12.8.2008






to my parents














Those who aspire not to guess and divine, but discover and know,
who propose not to devise mimic and fabulous worlds of their own,
but to examine and dissect the nature of this very world itself,
must go to the facts themselves for everything.

F. Bacon, 1620
Articles:
A. Petrov, K. A. Rufanov, V. V. Kotov, F. Laquai, J. Sundermeyer
A Lutetium Cyclopentadienyl-Phosphazene Constrained Geometry Complex (CGC): First
Isolobal Analoues of group 4 Cyclopentadienyl-Silylamino CGC Systems.
Eur. J. Inorg. Chem. 2005, 3805–3807.

A. R. Petrov, K. A. Rufanov, B. Ziemer, P. Neubauer, V. V. Kotov, J. Sundermeyer
P-Amino-cyclopentadienylidene-phosphoranes versus P-cyclopentadienyl-
iminophosphoranes – tautomeric protic forms of a new bidentate CpPN ligand system.
Dalton Trans. 2008, 909–915.

K. A. Rufanov, B. Ziemer, A. R. Petrov, K. Harms, J. Sundermeyer
Organophosphorus(V) ligands for coordination and organometallic chemistry. Part 7:
Synthesis and Molecular Structures of a Series of New Cyclopentadienyl-Phosphazene
Constrained-Geometry Complexes of Rare-Earth Metals.
Dalton Trans, 2008, submitted.

A. R. Petrov, K. A. Rufanov, K. Harms, J. Sundermeyer
Re-investigation of ortho-Metallated Dimethylbenzylamine Complexes of Rare-Earth Metals.
First Structurally Characterized Nd and Gd tetrakis-Arylates.
J. Organomet. Chem. 2008, submitted.

A. R. Petrov, J. Möbus, K. Harms, J. Sundermeyer
Synthesis and Chemistry of a New Highly Sterically Crowdered Cyclopentadienyl-
Phosphane.
J. Organomet. Chem. 2009, in preparation. Reports:
A. R. Petrov, K. A. Rufanov, J. Sundermeyer;
Rare-Earth Constrained-Geometry Complexes (CGC) with a New Cyclopentadienylidene-P-
Aminophosphorane (CpPN) Ligand System.
th18 Workshop on Rare Earth Chemistry: Terrae Rarae.
Universität zu Köln, Köln (Bonn-Röttgen), November 2005.

A. R. Petrov, K. A. Rufanov, J. Sundermeyer;
Exploration of Lanthanide (II, III) – CpPN – Complexes: Synthesis and Reactivity Studies,
th19 Workshop on Rare Earth Chemistry, Terrae Rarae.
Universität Oldenburg, Oldenburg, November 2006.

Poster Presentations:
K. A. Rufanov, A. Petrov, J. Sundermeyer
New Iminophosphonamide Ligands on the Basis of BINAMIN & TADDAMIN Auxiliaries.
thProceedings of the 12 Conference of the Inorganic Chemistry Division (Wöhler-Vereinigung
für Anorganische Chemie) of the GDCh
Philipps-Univeristät Marburg, Marburg, September 2004, P-048.

K. A. Rufanov, A. R. Petrov, J. Sundermeyer
New concept of ligand design for rare-earth and lanthanide organometallics.
thKeynote lecture, 17 Workshop on Rare Earth Chemistry and 1. Berichtskolloquium im
Rahmen des SPP 1166
Universität Bayreuth, Bayreuth, December 2004.

K. A. Rufanov, A. Petrov, J. Sundermeyer
Synthesis, Structures and Reactivity of a New Family of Cyclopentadienyl-Phospahazene
(“CpPN”) Constrained-Geometry Complexes (CGC)
of the Rare-Earth Metals (Sc, Y, Nd, Lu).
Proceedings of the Symposium of the Graduiertenkolleg 352.
Technische Universität Berlin, Berlin, November 2005. K. A. Rufanov, A. Petrov, J. Sundermeyer
Rare-Earth Constrained-Geometry Complexes (CGC) with a New Cyclopentadienylidene-P-
Aminophosphorane (“CpPN”) Ligand System.
thProceedings of the 18 Workshop on Rare Earth Chemistry.
Universität zu Köln, Köln (Bonn-Röttgen), December 2005.

A. Petrov, K. A. Rufanov
Lanthanide tris- and tetrakis- Aryl Complexes with pendant Dialkylamino Arms.
thProceedings of the 18 Workshop on Rare Earth Chemistry.
Universität zu Köln, Köln (Bonn-Röttgen), December 2005.

A. R. Petrov, J. Sundermeyer
Neue Herausforderungen in der metallorganischen Chemie mit Elementen der Gruppe 3 und
Lanthanoide. Cyclopentadienyl-Iminophphosphoran Constrained-Geometry Komplexe (CGC)
der Lanthanoiden.
GdCh Jahrestagung
Heinrich Heine Universität Düsseldorf, Düsseldorf, September 2005

K. A. Rufanov, A. R. Petrov
New hydroamination catalysts on the basis of tris- and tetrakis-aryl complexes of lanthanides
with chelating dialkylamino groups (in Russian).
International Symposium Advanced Science in Organic Chemistry (ACOS in Crimea 2006)
Sudak, Crimea, June 2006.

A. R. Petrov, O. Thomas, J. Sundermeyer
New, Homoleptic tris-Aryl Complexes of the Rare Earth Metals.
th20 Workshop on Rare Earth Chemistry, Terrae Rarae,
Universität zu Köln, Köln (Bonn-Röttgen), November, 2007. Acknowledgements
I would like to acknowledge everyone who extended their support and help during the course
of this work. My deep sense of gratitude goes to:

▫▪▫ Prof. Dr. Jörg Sundermeyer for a great opportunity to perform my PhD work in the
one of the best universities of Germany under his supervision and for establishing
an interesting research topic.
▪▫▪ Dr. Konstantin Rufanov for his introduction in practical organometallic chemistry
to me, interesting discussions all around chemistry as well as for a nice time in and
out side of laboratory.
▫▪▫ Prof. Dr. Andreas Seubert, Prof. Dr. Gerhard Hilt and Prof. Dr. Martin Broering
that they kindly agreed to familiarized themselves with my Thesis and to express
their opinion as scientific referees.
▪▫▪ Prof. (Emeritus) Manfred Meisel for his manificient support during my stay at his
research group in the Institut für Chemie der Humboldt-Universität zu Berlin.
▫▪▫ Dr. Klaus Harms for all X-ray structures he determined and solving computer
problems arose.
▪▫▪ Gertraud Geiseler for her patient and preparation of my very ″important″ crystals.
▪▫▪ Burkhard Ziemer and Petra Neubauer from the Institut für Chemie der Humboldt-
Universität zu Berlin for X-ray structure determination of crystals with the lowest
R-factor ever been seen at the department.
▫▪▫ Dr. Thomas Linder and Michael Elfferding for fast solution and refinement of a
numerous crystal data.
▫▪▫ Dr. Xiulan Xie for being ready to help to hold the stand-by modus on NMR
spectrometers.
▪▫▪ All colleagues of analytical laboratories of the department for spectroscopic
measurements even at holidays.
▪▫▪ My AFP colleagues – Drs. Christian Kleeberg and Thomas Linder – during the
time of inorganic practicum for precise organization and time management.
▫▪▫ Irene Barth for being actively involved in decision of any questions with respect to
the lab management – patience in preparation of huge amounts of the solvents
needed and holding order in our really big lab.

▫▪▫ Drs. Marat M. Khusniyarov and Katya Gauotchenova for their help in the creation
of reliable chemical database, typing and labeling of many thousands chemicals in
our laboratory.
▪▫▪ Dr. Daniel Gaess for instant holding of all three glove-boxes in running regime.
©▫▪▫ Jan Döring for his grateful help in any kind of problems with Microsoft and PC’s,
that ones saved a part of the work presented below.
†▪▫▪ Konstantin I. Smolko for interesting discussions in chemistry.
▪▫▪ All present and past PhD students I worked with: Marik, Alexey&Katja, Denis,
Nuri, Jan, Daniel, Thomas, Andi, Udo, Ralf, Wael, Fuming.
▪▫▪ All new PhD students that give start of the ″new age ″ in our laboratory: Marion,
Michael, Wolf, Olli, Nina and Kristina, Benjamin.
▫▪▫ All students worked with me during their AFP practicum for their patience in
complete analysis of a mass of new compounds synthesized.
▫▪▫ All my old and new friends I found in Moscow and Marburg.
▪▫▪ My mother Anastasia – who never prohibited my ″research ″ work in my ″hood″
at -50 °C and good chemical books and journals.
▫▪▫ My father Robert – who showed me that the world is bigger th