Homoleptic alkyl- and aryl-complexes of transition metals (Ti, Zr, Hf, Nb, and Cr)and tetra-organyloxyvanadium-(V) and -(IV) complexes [Elektronische Ressource] / by Said Mahmoud El-Kurdi
187 Pages
English

Homoleptic alkyl- and aryl-complexes of transition metals (Ti, Zr, Hf, Nb, and Cr)and tetra-organyloxyvanadium-(V) and -(IV) complexes [Elektronische Ressource] / by Said Mahmoud El-Kurdi

-

Downloading requires you to have access to the YouScribe library
Learn all about the services we offer

Description

Homoleptic Alkyl- and Aryl-Complexes of Transition Metals (Ti, Zr, Hf, Nb, and Cr) And Tetra-organyloxyvanadium-(V) and -(IV) Complexes Inaugural-Dissertation to obtain the academic degree Doctor rerum naturalium (Dr. rer. nat) submitted to the Department of Biology, Chemistry and Pharmacy of Freie Universität Berlin by Said Mahmoud El-Kurdi from Palestine Berlin, September 2010 "I humbly thank Allah Almighty, the Merciful and the Beneficent, who gave me health, thoughts and co-operative people to enable me achieve this goal." Dedication To the memory of my Father To the memory of my Brother, Mohammed To my mother, brothers and sisters To my wife To my children Areej, Mahmoud and Mohammed This work was completed under the supervision of Prof. Dr. K. Seppelt at the Institute of Inorganic and Analytical Chemistry of the Freie Universität Berlin. First Reviewer: Prof. Dr. K. Seppelt Second Reviewer: Prof. Dr. U. Abram Date of Defence: 07.10.2010 Acknowledgements I am heartily thankful to my supervisor, Prof. K. Seppelt, whose encouragement, guidance and support from the initial to the final level enabled me to develop an understanding of the subject. I would like to thank Prof. U. Abram for taking time out from his busy schedule to serve as my second examiner.

Subjects

Informations

Published by
Published 01 January 2010
Reads 30
Language English
Document size 3 MB


Homoleptic Alkyl- and Aryl-Complexes
of Transition Metals (Ti, Zr, Hf, Nb, and Cr)
And
Tetra-organyloxyvanadium-(V) and -(IV) Complexes





Inaugural-Dissertation

to obtain the academic degree
Doctor rerum naturalium (Dr. rer. nat)
submitted to the Department of Biology, Chemistry and Pharmacy
of Freie Universität Berlin
by
Said Mahmoud El-Kurdi
from Palestine



Berlin, September 2010




























"I humbly thank Allah Almighty, the Merciful and the Beneficent, who gave
me health, thoughts and co-operative people to enable me achieve this goal."






Dedication
To the memory of my Father
To the memory of my Brother, Mohammed
To my mother, brothers and sisters
To my wife
To my children Areej, Mahmoud and Mohammed









This work was completed under the supervision of
Prof. Dr. K. Seppelt
at the Institute of Inorganic and Analytical Chemistry
of the Freie Universität Berlin.



















First Reviewer: Prof. Dr. K. Seppelt
Second Reviewer: Prof. Dr. U. Abram
Date of Defence: 07.10.2010

Acknowledgements

I am heartily thankful to my supervisor, Prof. K. Seppelt, whose encouragement, guidance and
support from the initial to the final level enabled me to develop an understanding of the
subject.
I would like to thank Prof. U. Abram for taking time out from his busy schedule to serve as
my second examiner. A special thanks goes out to Dr. Spandel for measuring Raman
spectrum.
I would also like to thank all of my colleagues in our working group for the nice working
atmosphere built over the last 4 years. To all other people of the Inorganic building who
provided me valuable services during my research time.
I would like to express my gratitude to the DAAD for their financial support.
I also thank my mother, brothers and sisters for their never ending moral support and prayers
which always acted as a catalyst in my academic life.
I would like to thank my wife for supporting and encouraging me to pursue this degree.
Without my wife’s encouragement, I would not have finished this thesis.





During this research work the following publication and poster were done






Publication:
Said El-Kurdi, Abdal-Azim Al-Terkawi, Bernd M. Schmidt, Anton Dimitrov, and Konrad
Seppelt. Chem. Eur. J. 2010, 16, 595 – 599.



Poster:
Tungsten(VI) And Tungsten(V) Fluoride Complexes
Said El-Kurdi and Konrad Seppelt
th16 European symposium on fluorine chemistry, Ljubljana, Slovania july 18-23, 2010Table of Contents
I. Introduction ........................................................................................................................................... 1
II. General Background, Results and Discussion....................... 4
01. Homoleptic Penta- and Hexa- -Organyl d Metal Complexes ............................................................ 4
1.1 Nonoctahedral Structures of Hexacoordinate Homoleptic Complexes ............................................. 4
1.2 Homoleptic Pentacoordinate Complexes .......................................................... 7
2. Titanium Complexes ............................................................................................. 8
2.1 Pentaorganotitanium Complexes ....................................................................... 8
2.1.1 Synthesis and Characterization of Pentaphenyl- and Pentatolyltitanate(IV) . 9
2.1.2 Crystal Structure of [Li(THF) ][Ti(C H ) ] ....................................................................................... 10 4 6 5 5
2.1.3 Crystal Structure of [Li(Et O) ][Ti(p-C H -CH ) ] ............ 12 2 4 6 4 3 5
2.2 Hexa-aryltitanium(III) Complexes ..................................................................................................... 14
2.2.1 Synthesis and Characterization of Hexaphenyl- and Hexatolyltitanium(III) Complexes .............. 14
2.2.2 Crystal Structure of [Li Cl(THF) ][Ti(C H ) ] ................................................................................... 15 4 8 6 5 6
2.2.3 Crystal Structure of [Li Cl(Et O) ][Ti(p-C H -CH ) ] ........ 16 4 2 8 6 4 3 6
3. Zirconium and Hafnium Complexes ................................................................................................... 18
3.1 Zirconium Complexes ....................................................... 18
3.1.1 Pentaphenyzirconium(IV) Complex ............................................................................................... 19
3.1.1.1 Synthesis and Characterization of [NBu ][Zr(C H ) ]·4CH Cl .................... 19 4 6 5 5 2 2
3.1.1.2 Crystal Structure of [NBu ][Zr(C H ) ]·4CH Cl ........................................................................... 19 4 6 5 5 2 2
3.1.2 Hexaphenyl- and Hexatolylzirconium(IV) Complexes ... 21
3.1.2.1 Synthesis and Characterization of [Li(THF) ] [Zr(C H ) ] and [Li(Et O) ] [Zr(p-C H -CH ) ] ........ 23 4 2 6 5 6 2 4 2 6 4 3 6
3.1.2.2 Crystal Structure of [Li(THF) ] [Zr(C H ) ] ................................................................................... 23 4 2 6 5 6
3.1.2.3 Crystal Structure of [Li(Et O) ] [Zr(p-C H -CH ) ] ....... 25 2 2 2 6 4 3 6
3.2 Hafnium Complexes ......................................................................................................................... 28
3.2.1 Hexaphenyl- and Hexatolyl- Hafnium(IV) Complexes ................................... 28

i 3.2.1.1 Synthesis and Characterization of [Li(THF) ] [Hf(C H ) ] and [Li(THF) ] [Hf(p-C H -CH ) ]. ....... 28 4 2 6 5 6 4 2 6 4 3 6
3.2.1.2 Crystal Structure of [Li(THF) ] [Hf(C H ) ] .................................................................................. 28 4 2 6 5 6
4. Niobium Complexes ........................................................... 31
4.1 Hexaphenyl- and Hexatolylniobium(IV) Complexes ......................................................................... 32
4.1.1 Synthesis and Characterization of [Li (Et O) ][Nb(C H ) ] and [Li (Et O) ][Nb(p- C H -CH ) ] ...... 32 2 2 3 6 5 6 2 2 4 6 4 3 6
4.1.2 Crystal Structure of [Li (Et O) ][Nb(C H ) ]. .................................................................................. 32 2 2 3 6 5 6
4.1.3 Crystal Structure of [Li (Et O) ][Nb(p-C H -CH ) ]. ........ 35 2 2 4 6 4 3 6
5. Tetra- -organyloxovanadium Complexes .......................................................................................... 38
5.1 Reaction of VOCl with alkyl- and aryl lithium in presence of tmeda .............. 39 3
5.1.1 Synthesis of Tetra-methyloxyvanadium(V) Complex [Li Cl(tmeda) ][VO(CH ) ] ........................... 40 2 2 3 4
5.1.2 Crystal Structure of [Li Cl(tmeda) ][VO(CH ) ] .............................................................................. 40 2 2 3 4
2−5.2.1 Synthesis of Tetramethyl- and Tetraphenyl-oxyvanadium(IV) Complexes [VOL ] ..................... 42 4
5.1.2 Crystal Structure of [Li (THF) ][VO(CH ) ] ................................................................ 43 2 4 3 4
5.1.3 Crystal Structure of [Li (THF) ][VO(C H ) ] .................... 44 2 x 6 5 4
6. Chromium Complexes ........................................................................................................................ 45
6.1 Preparation of Tetra-alkyl chromium(IV) compounds: CrR ............................ 45 4
2 –6.2 Attempts to prepare CrR (R =CH , C H ) ....................................................................................... 45 6 3 2 5
6.3 Tetraisopropylchromium [Cr(i-prop) ] ............................. 46 4
6.3.1 Synthesis and Characterization Cr(i-C H ) .................................................................................... 46 3 7 4
6.3.2 Crystal Structure of Cr(i-C H ) ...................................................................................................... 46 3 7 4
III. Experimental Section ........................................................................................................................ 48
7. General Procedures ............................ 48
7.1 Abbreviations used ........................................................................................................................... 48
7.2 Instruments used ............................. 48
7.3 Experimental .................................................................................................................................... 49
8. Synthesis and Crystal Structure Analysis ............................ 50
8.1 Titanium Complexes ......................................................................................................................... 50

ii 8.1.1 [Li(THF) ][Ti(C H ) ] ........................................................................................................................ 50 4 6 5 5
8.1.1.1 Preparation of [Li(THF) ][Ti(C H ) ] ............................ 50 4 6 5 5
8.1.1.2 Crystal Data and Crystal Structure Analysis [Li(THF) ][Ti(C H ) ] ............................................... 51 4 6 5 5
8.1.2 [Li{(CH CH ) O} ][Ti(p-C H -CH ) ]. ................................................................................................ 56 3 2 2 4 6 4 3 5
8.1.2.1 Preparation of [Li{(CH CH ) O} ][Ti(p-C H -CH ) ]. ..... 56 3 2 2 4 6 4 3 5
8.1.2.2 Crystal Data and Crystal Structure Analysis of [Li{(CH CH ) O} ][Ti(p-C H -CH ) ]. .................... 57 3 2 2 4 6 4 3 5
8.1.3 Li ClTi(C H ) ·8(OC H ) .................................................................................................................. 67 4 6 5 6 4 8
8.1.3.1 Preparation of [Li Cl(THF) ][Ti(C H ) ] ........................ 67 4 8 6 5 6
8.1.3.2 Crystal Data and Crystal Structure Analysis of [Li Cl(THF) ][Ti(C H ) ] ....................................... 68 4 8 6 5 6
8.1.4 Li ClTi(p-C H -CH ) ·8(Et O) ........................................................................... 77 4 6 4 3 6 2
8.1.4.1 Preparation of [Li Cl(Et O) ][Ti(p-C H -CH ) ] ............................................. 77 4 2 8 6 4 3 6
8.1.4.2 Crystal Data and Crystal Structure Analysis of [Li Cl(Et O) ][Ti(p-C H -CH ) ] ........................... 77 4 2 8 6 4 3 6
8.2 Zirconium Complexes ....................................................................................................................... 84
8.2.1 [NBu ][Zr(C H ) ]·4CH Cl .............. 84 4 6 5 5 2 2
8.2.1.1 Preparation of [NBu ][Zr(C H ) ]·4CH Cl ................................................................................... 84 4 6 5 5 2 2
8.2.1.2 Crystal Data and Crystal Structure Analysis of [NBu ][Zr(C H ) ]·4CH Cl .................................. 85 4 6 5 5 2 2
8.2.2 [Li(THF) ] [Zr(C H ) ] ...................................................................................................................... 93 4 2 6 5 6
8.2.2.1 Preparation of [Li(THF) ] [Zr(C H ) ] ........................... 93 4 2 6 5 6
8.2.2.2 Crystal Data and Crystal Structure Analysis of [Li(THF) ] [Zr(C H ) ] ......................................... 94 4 2 6 5 6
8.2.3 [Li (Et O) ][Zr(4-C H -CH ) ] ......................................................................... 107 2 2 4 6 4 3 6
8.2.3.1 Preparation of [Li (Et O) ][Zr(4-C H -CH ) ] ............................................. 107 2 2 4 6 4 3 6
8.2.3.2 Crystal Data and Crystal Structure Analysis of [Li (Et O) ][Zr(4-C H -CH ) ] ............................ 108 2 2 4 6 4 3 6
8.3 Hafnium Complexes ....................................................................................................................... 121
8.3.1 [Li(THF) ] [Hf(C H ) ] ................... 121 4 2 6 5 6
8.3.1.1 Preparation of [Li(THF) ] [Hf(C H ) ] ........................................................................................ 121 4 2 6 5 6
8.3.1.2 Crystal Data and Crystal Structure Analysis of [Li(THF) ] [Hf(C H ) ] ....................................... 121 4 2 6 5 6
8.3.2 [Li(THF) ] [Hf(p-C H -CH ) ] ......................................................................... 127 4 2 6 4 3 6

iii 8.3.2.1 Preparation of [Li(THF) ] [Hf(p-C H -CH ) ] .............................................................................. 127 4 2 6 4 3 6
8.4 Vanadium complexes ..................................................... 128
8.4.1 [Li(tmeda)][VO(CH ) ]·LiCl(tmeda) .............................................................................................. 128 3 4
8.4.1.1 Preparation of [Li(tmeda)][VO(CH ) ]·LiCl(tmeda) ................................... 128 3 4
8.4.1.2 Crystal Data and Crystal Structure Analysis of [Li(tmeda)][VO(CH ) ]- LiCl(tmeda) ................. 128 3 4
8.4.2 [Li (THF) ][VO(CH ) ] ................................................................................................................... 132 2 4 3 4
8.4.2.1 Preparation of [Li (THF) ][VO(CH ) ] ........................ 132 2 4 3 4
8.4.2.2 Crystal Data and Crystal Structure Analysis of [Li (THF) ][VO(CH ) ] ....................................... 133 2 4 3 4
8.4.3 [Li (THF) ][VO(C H ) ] .................................................................................. 139 2 x 6 5 4
8.4.2.1 Preparation of [Li (THF) ][VO(C H ) ] ....................................................... 139 2 x 6 5 4
8.4.2.2 Crystal Data and Crystal Structure Analysis of [Li (THF) ][VO(C H ) ] ...................................... 140 2 x 6 5 4
8.5 Niobium Complexes ....................................................................................................................... 147
8.5.1 [Li (Et O) ][Nb(C H ) ] ................. 147 2 2 3 6 5 6
8.5.1.1 Preparation of [Li (Et O) ][Nb(C H ) ] ...................................................................................... 147 2 2 3 6 5 6
8.5.1.2 Crystal Data and Crystal Structure Analysis of [Li (Et O) ][Nb(C H ) ] ..................................... 147 2 2 3 6 5 6
8.5.2 [Li (Et O) ][Nb(p-C H -CH ) ] ....................................................................... 154 2 2 4 6 4 3 6
8.5.2.1 Preparation of [Li (Et O) ][Nb(p-C H -CH ) ] ............................................ 154 2 2 4 6 4 3 6
8.5.2.2 Crystal Data and Crystal Structure Analysis of [Li (Et O) ][Nb(p-C H -CH ) ]........................... 154 2 2 4 6 4 3 6
8.6 Chromium Complexes .................................................................................................................... 165
8.6.1 Cr(i-C H ) .................................................................................................................................... 165 3 7 4
8.6.1.1 Preparation of Cr(i-C H ) ......... 165 3 7 4
8.6.1.2 Crystal Data and Crystal Structure Analysis ............................................................................. 165
IV. Summary ......................................................................... 169
V. Zusammenfassung ........................................................................................................................... 171
VI. References ...................................... 173

iv