Investigations of the reactivity of Bis(trichlorostannyl)organyl compounds [Elektronische Ressource] / vorgelegt von Hari Pada Nayek

H P Nayek

Informations

• Publié par: philipps-universitat_marburg
• Publié le: 01 janvier 2009
• Nombre de lectures: 18
• Langue: English
• Poids de l'ouvrage: 11 Mo

Extrait

Investigations of the Reactivity of
Bis(trichlorostannyl)organyl Compounds



DISSERTATION

zur Erlangung des akademischen Grades eines
DOKTORS DER NATURWISSENSCHAFTEN
(Dr. rer. nat.)

dem Fachbereich Chemie
der Philipps-Universität Marburg
vorgelegt von


Hari Pada Nayek, M.Sc.
aus Howrah, Indien
Marburg/Lahn 2009











Die vorliegende Arbeit entstand in der Zeit von August 2006 bis July 2009 unter der
Anteitung von Frau Prof. Dr. Stefanie Dehnen am Fachbereich Chemie der Phillips-
Universität Marburg.



1. Gutachter: Prof. Dr. S. Dehnen
2. Gutachter: Prof. Dr. J. Sundermeyer

Tag der mündlichen Prüfung:






Dedicated to my parents




















The extraordinary does not happen on plain, ordinary ways
Johann Wolfgang von Goethe











Acknowledgements

The research presented in this thesis would not have been possible without the generous
help and support of many people. In this section I would like to thank and acknowledge
all of them.
Firstly, I would like to thank my advisor Prof. Dr. Stefanie Dehnen for her intellectual
and professional guidance, for the opportunity to work in an exciting research group, for
involving me in the preparation of many manuscripts, and especially for allowing me a
large degree of independence and creative freedom to explore a wide range of synthetic
aspirations.
I am grateful to Prof. Jörg Sundermeyer, who commented on my research and reviewed
the thesis.
I would also like to express my thanks to Prof. Dr. Werner Massa and Dr. Klaus Harms
for helping me in crystal structure analysis and Frau Geiseler for collecting single crystal
data.
I would like to thank Dr. Frank Weller, Fritjof Schmock and Cornelia Mischke, who
provided me with valuable results in the IR and Raman spectroscopy analyses.
I am grateful to Dr. Seema Agarwal for her help with thermogravimetric analyses.
I would like to thank Clemens Pietzonka for recording EDX spectra and for teaching me
how to measure EDX.
I am grateful to my students, Stefanie Uhlmann, Leonid Schaaf, Stephan Hammer, Wang
Di and Heinke Thrun for synthesizing a lot of compounds.
I would like to thank all past and present members of the Dehnen research group, Ursula
Siepe, Dr. Maike Melullis, Dr. Eugen Ruzin, Dr. Sima Haddadpour, Dr. Zhien Lin, Dr.
Reza Halvagar, Susanne Burtzlaff, Heiko Niedermeyer, Felicitas Lips, Zohre
Hassanzadeh, Johanna Heine, Samuel Heimann, Christopher Pöhlker, Thomas Kaib,
Günther Theile, Birte Seibel and Sabrina Peter.
I wish to thank my friends from Marburg and rest of the world for their suggestions and
cooperations.
I wish to thank my mother, my brothers, my uncle and my whole family for constant
long-distance support, personal inspiration, and so much more that I can not explain here.
Finally, thank you very much God for making my life simple, peaceful and enjoyable.
Table of Contents

1 Introduction…………………………………...............1
1.1 Tin…………………………………………………………………………..1
1.1.1 Occurrence………………………………………………………………….1
1.1.2 Physical Properties of Metallic Tin………………………………………....2
1.1.3 Chemical Properties………………………………………………………...3
1.2 Inorganic Tin Chalcogen Compounds……………………………………...3
1.2.1 Chalcogenidostannates……………………………………………………..3
1.2.2 Ternary Tin Chalcogenide Clusters………………………………………...6
1.3 Organotin Compounds……………………………………………………..10
1.3.1 Organotin Chalcogenide Compounds……………………………………...11
1.3.2 Organotin Ternary Clusters………………………………………………...14

2 Research Objectives………………………………….19
3 Results and Discussion……………………………….21
3.1 Reactivity of Bis(trichlorostannyl)organyls toward Chalcogenide
and Chalcogenolates………………….……………………………………21
3.1.1 Reactivity of Bis(trichlorostannyl)organyls toward Chalcogenides……….21
3.1.2 Reactivity ofrostannyl)organyls toward Thiolates……….…….25
3.1.2.1 Characterization of Bis[tris(thioaryllato)stannyl]organyls (R'S) Sn–R–3
Sn(SR') with R', R = Ph, 1,4-Bu (1), Ph, 1,4-Dimethylbenzene (2), 3
Ph, 4,4'-Dimethylbiphenyl (3), 2-Naphthyl, 1,4-Bu (4) and 2-Naphthyl,
1,4-Dimethylbenzene (5)…………………………………………………..26
3.1.3 Reactivity of Bis(trichlorostannyl)organyls toward Selenolates…………..32
3.1.3.1 Characterization of (PhSeCl )Sn–(CH ) –Sn(Cl SePh) (6) and 2 2 4 2
(R'Se) Sn–R–Sn(SeR') R', R = Ph, 1,4-Bu (7), 1-Naphthyl, 1,4-Bu (8) 3 3
Ph, 1,4-Dimethylbenzene (9), Ph, 1,1'-Ferrocenyl (10), 1-Naphthyl,
1,1'-Ferrocenyl(11)………...………………………………………………33
3.1.4 NMR Spectroscopy………………………………………………………...40
3.1.5 Quantum Chemical Study…………………………………………………..40
3.2 Stability and Reactivity of Bis[tris(arylchalcogenolato)stannyl]organyls…43
3.2.1 Thermolysis of Bis[tris(arylchalcogenolato)stannyl]organyls……………..43
3.2.2 Reactivity of Bis[tris(arylchalcogenolato)stannyl]organyls……………….44
3.2.2.1 Synthesis and Characterization of [Pd(SePh)(OAc)] (12)………………...45 4
3.2.2.2 Quantum Chemical Study of Compound 12……………………………….50
3.3 Reactivity of Bis(trichlorostannyl)organyls toward PhSeSiMe and 3
Coinage Metal Complexes…………………………………………….…...55
3.3.1 Synthesis and Characterization of [(Ph P) (SePh) Cu ]·1.5THF (13·1.5 3 3 2 2
THF)………………………………………………………………………..55
3.3.2 Synthesis and Characterization of [(Ph PAg) Ag ( μ –Se) (SePh) ][R SnCl ] 3 8 6 6 1-x/2 12 3 2
(x = 0 (14), 1; R = Ph (15), Cy (16))…………………………………………....60
3.3.3 Quantum Chemical Study of Compounds 14-16……………..……………67
3.4 Reactivity of Bis(trichlorotin)organyls under Solvothermal Conditions......70
13.4.1 Synthesis and Characterization of [SnS ·en] (17)………….…………….71 2 ∞
3.4.2 Synthesis and Characterization of [enH] [Sn S ]·en (18)………………….73 4 2 6
3.4.3 Optical Absorption Behavior of Compounds 17 and 18……………...……76
3.4.4 Synthesis and Characterization of [(Ph PCu) {cyclo-(CH ) SnS } Cu Sn] 3 6 2 4 2 6 4
(19)…………………………………………………………………………77
3.4.5 Quantum Chemical Investigation of Compound 19………….………...….81

4 Experimental Section……………………………...…85
4.1 General Aspects……………………………………………………………85
4.1.1 Working Techniques……………………………………………………….85
4.1.2 Solvents…………………………………………………………………….85
4.1.3 Spectroscopic Studies……………………………………………………...86
4.1.4 Quantum Chemical Investigation………………………………………… 86
4.2 Synthesis of Staring Materials……………………………………………..88
4.2.1 Chemicals Used……………………………………………………………88
4.2.2 Synthesis of 1,4-Bis(triphenylstannyl)butane……………………………...88
4.2.3 Synthesis of 1,4-Bis(trichlorostannyl)butane………………………………89
4.2.4 Synthesis of 1,4-bis(tricyclohexylstannylmethyl)benzene………………...90
4.2.5 Synthesis of 1,4-bis(trichlorostannylmethyl)benzene……………………...91
4.2.6 Synthesis of 4,4'-Bis(tricyclohexylstannylmethyl)biphenyl……………….91
4.2.7 Synthesis of 4,4´-bis(trichlorotinmethyl)biphenyl…………………………92
4.2.8 Synthesis of 1,1'-dilithioferrocene·TMEDA……………………………….93
4.2.9 Synthesis of 1,1'-Bis(trimethylstannyl)ferrocene………………………….93
4.2.10 Synthesis of 1,1'-Bis(chlorodimethylstannyl)ferrocene……………………94
4.2.11 Synthesis of 1,1'-Bis(trichlorostannyl)ferrocene…………………………..95
4.2.12 Synthesis of tris(triphenylphosphine)copper(I)chloride…………………...95
4.2.13 Synthesis of tris(triphenylphosphine)silver(I)nitrate………………………96
4.3 Synthesis of Novel Compounds……………………………………………97
4.3.1 Synthesis of Polymeric Solid………………………………………….…...97
4.3.2 Synthesis of 1,4-Bis[tris(thiophenolato)stannyl]butane (1)………………..97
4.3.3 Synthesis of 1,4-Bis[tris(thiophenolato)stannylmethyl]benzene (2)………98
4.3.4 Synthesis of 4,4'-Bis[tris(thiophenolato)tinmethyl]biphenyl (3)…………..99
4.3.5 Synthesis of 1,4-Bis[tris(thionaphthylato)stannyl]butane (4)…………….100
4.3.6 Synthesis of 1,4-Bis[tris(thionaphthylato)st