Synthesis of Gyroscope-like Molecules via Alkene - Opus4.kobv.de

204 Pages·2007·8.84 MB·English

Synthesis of Gyroscope-like Molecules via Alkene
Metathesis. Facile Substitution and Demetalation,
and a Search for Cage Effects

Den Naturwissenschaftlichen Fakultäten der
Friedrich-Alexander-Universität Erlangen-Nürnberg
zur
Erlangung des Doktorgrades

vorgelegt von

Agnieszka Joanna Nawara-Hultzsch

aus Bytom, Polen
Als Dissertation genehmigt von den Naturwissenschaftlichen
Fakultäten der Universität Erlangen-Nürnberg

Tag der mündlichen Prüfung: 23.01.2008

Vorsitzender
Der Promotionskommission: Prof. Dr. E. Bänsch

Erstberichterstatter: Prof. Dr. J. A. Gladysz

Zweitberichterstatter. Prof. Dr. H. Kisch
Habe nun, ach! Philosophie,
Juristerei und Medizin,
Und leider auch Theologie!
Durchaus studiert, mit heißen Bemühn.
Da steh ich nun, in armer Tor!
Und bin so klug als wie zuvor ...

Faust, Johann Wolfgang Goethe

Für meinen besten Freund und meinen Mann Kai

A cknowledgments

I wish to thank Prof. John A. Gladysz for his acceptance in his research group and
for the interesting research project.

I would like to thank Dr. "Pepe" Giner Planas for his introduction to Schlenk
techniques, generous support during my PhD, and for his friendship. I would like to thank
Prof. Leyong Wang for scientific discussions and sharing the joy of science.

I want to thank my friends Dr. Joanna Sawiec, Agnieszka Kopczyńska and Janina
Kornas for their friendship, support and for all social events that we shared together.
Special thanks to Dr. Maria Wolak and Joanna Procelewska for their help during my
residence in Erlangen.

I would like to thank all my colleagues and friends: Patricia Horrilo Martínez (fun),
Carola Ganzman (teaching together and discussions), Dr. Qinglin Zheng (scientific
advices), Dr. Gareth Owen, Dr. Rosenildo Costa, Dr. Roland Gröbl, Dante Castilio Molena
(bicycle tours), Gisela Hess, Gampiero Racchiero (trip to Italy), Michal Barbasiewicz (cafe
time). All past and current co-workers from the JAG group I would like to thank for the
barbecue/E-Werk/cake events.

Dr. Alena Slezak, Margarete Dziallach and Hannelore Oschman for support (sweets
and fruits) and advice: special thanks.

All employee of the Organic Institute for the help and technical support: Prof.
Walter Bauer (scientific discussion, 31P EXSY), Dr. Frank Hampel, Wolfgang
Donaubauer, Dr. habil. Sławomir Szafert (Wrocław University) and Prof. Tadeusz Lis
(Wrocław University) (X-Ray analysis), Wilfried Schätzke and Christian Placht (NMR
spectroscopy), Eva Hergenröder (elemental analysis), Margerate Dziallach and Wolfgang
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Donaubauer (MS spectrometry), Stefan Fronius and Bahram Saberi (glassblowers), Erwin
Schreier and Eberhard Rupprecht (machine shop), Nicole Thomas, Pamela Engerer, Birgit
Haltrich and Christiane Brandl-Rittel (secretariat).

From deepest of my hart I would like to thank my Polish family: my father
Mieczysław and brothers: Grzegorz and Leszek with his wife Teresa and sons Marcin and
Karol for ongoing support and help. Also my German family: my parents in law Elsbeth
and Klaus and my sister in law Karen thanks for everything what I had privilege to share
with them. Beside all of this, both families and my mother Barbara special thanks for the
love that was given to me through all the years.

My husband Kai for his love and friendship, for which I am very thankful.

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Table of Contents
Acknowledgments iii
Abstract viii
Zusammenfassung x
List of Tables xii
List of Figures xiv
List of Schemes xvii
List of Abbreviations xx
List of Compounds xxii

1 General Introduction 1
1.1 Molecular Devices, Single Molecular Machines 1
1.2 The Gyroscope as a Macroscopic Device 5
1.3 Gladysz - type Molecular Gyroscopes 6
1.4 Aim of This Work 8
1.5 References 9
2 Application of Ring Closing Metathesis for Synthesis of Square
Planar Gyroscope-like Molecules 11
2.1 Introduction 11
2.2 Results 12
2.2.1 Synthesis of trans-MX (PR ) Precursors 12
2 3 2
2.2.2 Macrocyclization by Ring Closing Metathesis and 17
Hydrogenation
2.3 Discussion 31
2.3.1 Metathesis Reaction 31
2.3.2 Geometry and Chain Length Effect 34
2.3.3 Spectroscopy 38
2.3.4 Mass Spectra and Thermal Stability 41
2.3.5 Conclusions 41
v
2.4 Experimental Section 43
2.5 References and Notes 61
3. Rotation Control in Square Planar PdX /PtX Complexes:
2 2
Substitution Reactions of Gyroscope-like Molecules 64
3.1 Introduction 64
3.2 Results 66
3.2.1 Syntheses of Halide, Cyanide, Thio/Isothiocyanide and Phenyl
Derivatives 66
3.2.2 Synthesis of Unsymmetrically Substituted Gyroscope-like
Molecules 90
3.2.3 Demetalation 94
3.2.3.1 Demetalation Reactions - Free Diphosphine 98
3.3 Discussion 104
3.3.1 Complex Syntheses 104
3.3.2 NMR- Spectra and Dynamic Properties 105
3.3.3 Crystal Structures 109
3.3.4 The Cage Diphosphine 127
3.3.5 Conclusions 130
3.4 Experimental Section 132
3.5 References and Notes 145
4. Effect of Gyroscope Cage upon Reactivity 149
4.1 Introduction 149
4.2 Results 149
4.2.1 Synthesis of trans-PtCl (P(CH CH ) ) and Substitution
2 2 3 3 2
Reactions 149
4.2.2 Kinetics of Substitution Reactions 152
4.3 Discussion 158
4.3.1 Cis/trans Equilibria 158
4.3.2 Mechanistic Aspects 159
vi
4.3.3 Rate of Substitution Reactions 160
4.3.4 Conclusions 160
4.4 Experimental 161
4.4.1 Syntheses 161
4.4.2 Rate Measurements 162
4.5 References and Notes 164
5. Crystallography 166
5.1 Data Collection and Structure Refinement 166
5.2 Data Deposition 167
5.3 Crystallographic Tables 170
Lebenslauf 177
Publication List 178

vii
Abstract

Reactions of Br(CH ) CH=CH (n = 4, a; 5, b; 6, c; 7, d; 8, e; n = 6, 7 prepared
2 n 2
from Br(CH ) Br and t-BuOK) with Mg and then PCl (0.33 equiv) give phosphines
2 n+2 3
P((CH ) CH=CH ) (2a-e, 52-88%). Reactions of 2a-c,e with PdCl (COD) give trans-
2 n 2 3 2
PdCl ((P(CH ) CH=CH ) ) (trans-3a-c,e, 35-92%) and 2a-c with PdBr (COD) give
2 2 n 2 3 2 2
trans-PdBr ((P(CH ) CH=CH ) ) (trans-4a-c, 49-61%). When PtCl is treated with 2c-e
2 2 n 2 3 2 2
in C H , trans-PtCl ((P(CH ) CH=CH ) ) (trans-5c-e, 41-75%) is formed selectively.
6 6 2 2 n 2 3 2
Alkene metathesis of trans-3a,b and trans-4a,b using Ru(=CHPh)(PCy ) (Cl)
3 2 2
produced polymers. Analogous reactions of trans-3c,e and trans-5c-e yield mixtures of
cyclic isomers. Hydrogenations of the metathesis products with RhCl(PPh ) (H , 5 bar)
3 3 2
yield crude product mixtures (45-85%). Column chromatography gives trans-
MCl (P((CH ) ) P) (M = Pt, 6c-e, 4-43%; M = Pd, 7c,e, 15-37%) and the isomers
2 2 2n+2 3
trans-MCl (P(CH ) CH )((CH ) )(P(CH ) CH ) (M/n = Pt/7, 6'd, 4%; Pt/8,
2 2 2n+1 2 2 2n+2 2 2n+1 2
6'e, 21%; Pd/8, 7'e, 3%). The crystal structures of 6c and 7c are determined and discussed.
Reactions of trans-MCl (P((CH ) ) P) with LiBr, NaI and KCN give trans-
2 2 2n+2 3
MX (P((CH ) ) P) (M/X/n = Pt/Br/6, 10c, 75%; Pt/I/6, 11c, 58%; Pt/CN/6, 14, 91%;
2 2 2n+2 3
Pt/CN/8, 16, 82%; Pd/Br/6, 8c, 99%; Pd/I/6, 9c, 92%; Pd/CN/6, 15, 86%; Pd/Br/8, 12e,
70%; Pt/I/8, 13e, 82%). The crystal structures of 8c, 9c, 10c, 11c are determined and
discussed.
Reaction of 6c with KSCN gives two linkage isomers, trans-
Pt(NCS) (P((CH ) ) P) (17, 18%) and trans-Pt(NCS)(SCN)(P((CH ) ) P) (18, 21%).
2 2 14 3 2 14 3
Reactions of 6c and 6e with Ph Zn yield trans-Pt(C H ) (P((CH ) ) P) (19, 60%; 20,
2 6 5 2 2 2n+2 3
90%), which are treated with 1.0 equiv of HCl to give unsymmetrically substituted trans-
PtCl(C H )(P((CH ) ) P) (21, 93%; 22, 99%). The crystal structures of 17, 19-21 are
6 5 2 2n+2 3
determined and discussed.
Reaction of 6c with an excess of NaC≡CH gives the diphosphine P((CH ) ) P (23,
2 14 3
66%). When 14 is treated with KCN, 23 is isolated in 83% yield. Treatment of 6c with 4.5
equiv of LiC≡CPh affords 23 (86%) and Li [Pt(C≡CPh) ]THF (25, 51%).
2 4 2
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