Syntheses, structures and properties of metal complexes of bis(2-pyridylmethyl) derivatives of o-, m-, and p-phenylenediamine and aniline [Elektronische Ressource] / vorgelegt von Sabrina Turba

Informations

• Publié par: justus-liebig-universitat_giessen
• Publié le: 01 janvier 2008
• Nombre de lectures: 11
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

JUSTUS-LIEBIG-UNIVERSITÄT GIESSEN
INSTITUT FÜR ANORGANISCHE UND ANALYTISCHE CHEMIE







Syntheses, structures and properties of metal complexes
of bis(2-pyridylmethyl) derivatives of o-, m-, and p-
phenylenediamine and aniline
Inaugural-Dissertation

zur Erlangung des Doktorgrades der Naturwissenschaften im Fachbereich Biologie
und Chemie der Justus-Liebig-Universität Gießen




vorgelegt von




Sabrina Turba

aus

Gießen















































Erstgutachter: Prof. Dr. Siegfried Schindler

Zweitgutachter: Prof. Dr. Richard Göttlich

Abgabe der Dissertation im Prüfungsamt: 22.01.2008

Tag der mündlichen Prüfung: 29.02.2008





















For my parents



Acknowledgements

The work described in this doctoral thesis has been carried out between December
2004 and February 2008 at the Institute of Inorganic and Analytical Chemistry at the
Justus-Liebig-University of Gießen under the supervision of Prof Dr. Siegfried
Schindler.

I would like to express my sincere gratitude to my supervisor Prof. Dr. Siegfried
Schindler for his excellent guidance and for his great support, patience and
enthusiasm during these years.

Furthermore I wish to thank my colleagues and labmates Anja Henss, Sandra
Kisslinger, Alexander Beitat, Jörg Müller (every work group deserves a person like
him), Thomas Nebe, Christian Würtele, Tobias Hoppe, Dr. Jing-Yuan Xu, Dr. Ildikó
Kerezsi, Dr. Jörg Astner, Janine Will, Sabrina Schäfer and Tatjana Neuwert for their
friendship and encouragement. We shared rooms, discussions and litres of sparkling
wine. Thank you for a great time!

I would like to express my gratitude to Christian Würtele and Dr. Olaf Walter for their
friendly support in handling out the X-Ray Crystallography.

Furthermore I would like to thank the people of the Institute of Inorganic and
Analytical Chemistry and of the Institute of Organic Chemistry at the Justus-Liebig-
University in Gießen for their support of my work

Surely my words will not encompass the love and gratitude that I have for my friends
and family who have influenced my life and have formed me to the person I am now.
I will not list them here purely out of confidence that they know who they are.

Unfortunately, most of the endeavors that one would like to undertake are loaded
with financial barriers. For the reduction of these barriers I owe my parents a big
IOU.
I Ligand precursors used


1,3-Phenylendiamine Aniline



NH 2
HNNH2 2




1,3,5-Triaminobenzene trihydrochloride 2,6-Diamino-p-cresole dihydrochloride



NH CH2 3
* 3 HCl * 2 HCl
HNNH2 2 H N NH 2 2
OH



2-(Chloromethyl)pyridine hydrochloride 1,2-Phenylendiamine




* HCl
NCHCl2 HNNH2 2
II Ligands used
Ligands used

N, N-Bis(2-pyridylmethyl)aniline 1,2-Bis[bis(2-
(phbpa) pyridylmethyl)amino]benzene
(1,2-tbpd)



NN N N
N
N
N
NN


1,3-Bis[bis(2- 1,4-Bis[bis(2-
pyridylmethyl)amino]benzene pyridylmethyl)amino]benzene
(1,3-tbpd) (1,4-tbpd)


N NNN
NNN
N N
N
NN


1,3,5-Tris[bis(2- 2,6-Bis[bis(2-pyridylmethyl)amino]-p-
pyridylmethyl)amino]benzene cresole
(1,3,5-hpbt) (2,6-tpcd)


CHN N 3
N
NNN N
OH
N N
NNN
N
N N

III Abbreviations

d Doublet (NMR)
dd of Doublet (NMR)
δ chemical shift in ppm (NMR)
DMSO Dimethylsulfoxide
e. g. for example (Latin: exempli gratia)
1{H} Proton-decoupled (NMR)
Hc Hemocyanin
IR Infrared
m Multiplet
MeOH Methanol
NMR Nuclear Magnetic Resonance
Ph Phenyl
RT Room temperature
s Singlet (NMR)
t Triplet
TLC Thin Layer Chromatography
UV/Vis Ultraviolet-visible

























IV Table of contents

Acknowledgements ..................................................................................................... I
Ligand precursors used .............................................................................................. II
Ligands used ............................................................................................................. III
Abbreviations IV
Table of contents ........................................................................................................ V
Table of Figures and Schemes................................................................................ VIII
Chapter 1 - Introduction 1
1.1 Motivation 1
1.2 Copper proteins. .............................................................................................. 1
1.3 Model complexes for copper proteins .............................................................. 2
1.4 m-phenylendiamine based ligands................................................................... 3
1.5 Magnetic properties of copper(II) complexes with the ligand 1,3-tpbd. ............ 5
1.6 Projects............................................................................................................ 6
1.6.1 Metal complexes with the ligand 1,3-tpbd................................................. 6
1.6.2 Copper(II) complexes with derivatives of the ligand 1,3-tpbd. .................. 7
Chapter 2 - Syntheses and Characterisation of Copper(II) Complexes with the Ligand
1,3-Bis[bis(2-pyridylmethyl)amino]benzene (1,3-tpbd). .............................................. 9
2.1 Introduction ...................................................................................................... 9
2.2 Results and Discussion.................................................................................. 10
2.2.1 Syntheses............................................................................................... 10
2.2.2 [Cu (1,3-tpbd) (H O) (NO ) ](NO ) x 13 H O (1).................................... 11 4 2 2 4 3 4 3 4 2
2.2.3 [Cu (1,3-tpbd) (AsO )(ClO ) (H O)](ClO ) x 2 H O x 0.5 CH OH (2)..... 12 4 2 4 4 3 2 4 2 2 3
2.2.4 [Cu (1,3-tpbd) (PO )(ClO ) (H O)](ClO ) x 2 H O x 0.5 CH OH (3)....... 13 4 2 4 4 3 2 4 2 2 3
2.2.5 [Cu (1,3-tpbd)((PhO) P(O) ) ] (ClO ) (4)............................................... 15 2 2 2 2 2 4 4
2.2.6 [Cu (1,3-tpbd)((PhO)PO ) (H O) (CH CN) ] (BPh ) x Et O x CH CN 2 3 2 2 0.69 3 0.31 2 4 4 2 3
(5). 16
2.3 Magnetic Measurements................................................................................ 17
2.4 Conclusion ..................................................................................................... 19
2.5 Experimental Section..................................................................................... 19
2.5.1 General Remarks.................................................................................... 19
2.5.2 Ligand synthesis..................................................................................... 20
2.5.3 Complex Syntheses................................................................................ 20
2.5.4 Magnetic Measurements. ....................................................................... 21
2.5.5 X-ray Crystallographic Studies................................................................ 21
Chapter 3 - Syntheses, structures and properties of copper(II) complexes of bis(2-
pyridylmethyl) derivatives of o-, m-, and p-phenylenediamine and aniline................ 26
3.1 Introduction .................................................................................................... 26
3.2 Results and Discussion.................................................................................. 28