New model compounds for molecular devices [Elektronische Ressource] : novel methodologies that afford linear Pt_1tnyC_1tnx species consisting of 2-4 platinum atoms and up to 28 sp-hybridized carbon atoms / Qinglin Zheng

Ak Gladysz

Informations

• Publié par: friedrich-alexander-universitat_erlangen-nurnberg
• Publié le: 01 janvier 2005
• Nombre de lectures: 23
• Langue: Deutsch
• Poids de l'ouvrage: 1 Mo

Extrait

New Model Compounds for Molecular Devices:
Novel Methodologies that Afford Linear Pt C Species y x
Consisting of 2-4 Platinum Atoms and up to 28 sp-
Hybridized Carbon Atoms

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

vorgelegt von
Qinglin Zheng
aus VR China










Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der
Universität Erlangen-Nürnberg














Tag der mündlichen Prüfung:05.08.2005

Vorsitzender der Promotionskommission: Prof. Dr. D.-P. Häder
Erstberichterstatter: Prof. Dr. J. A. Gladysz
Zweiterberichterstatter: Prof. Dr. A. Hirsch
Drittberichterstatter: Prof. M. G. Humphrey





ii Für meine Frau und meine Söhne


























iii Danksagung

Die vorliegende Arbeit wurde unter Anleitung von Prof. Dr. J. A. Gladysz am Institut
für Organische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg in der Zeit
von November 2000 bis September 2004 angefertigt. Ich danke Prof. Gladysz für die Stellung
des interessanten Themas und sein Interesse am Fortgang der Arbeit sowie die fachliche und
finanzielle Unterstützung.

Mein ganz besonderer Dank gilt meinen Kollegen und Freunden Dr. H. Jiao, Dr. K.
Hultzsch, M. Wende, W. Mohr, J. Stahl für die zahllosen Diskussionen und F. Friedlein, Dr.
F. Zhuravlev, Dr. T. Shima, G. Racchiero, R. Costa, S. Eichenseher, L. de Quadras, A.
Nawara, R. Gröbl, C. Emnet sowie anderen Kollegen für die nette Arbeitsatmosphäre und
vielfältige Bier-/Grill/Film/Fußball/Fahrradtour-Events, die mir viel Spaß gemacht haben.

Herzlichster Dank gebührt den Angestellten des Organischen Instituts für die
unterschiedlichste Art der Hilfe: Dr. W. Bauer, W. Schätzke und C. Placht für die geduldige
Einführung am GX 400 Monster und das Anfertigen einiger NMR Spektren, Dr. F. Hampel
für die Röntgenstrukturanalyse, E. Hergenröder für die Elementaranalysen, W. Donaubauer
für die Massenspektren, S. Fronius für die Erstellung und Reparatur von Glasgeräte, E.
Schreier und K. Rupprecht von der Werkstatt und allen beteiligten Sekretärinnen.

Dank geht auch an meinen Studienkollegen A. Franz und J. Schmidt für Ihre
Ermutigung und Hilfe.

Mein allergrößter Dank geht von ganzem Herzen an meine Frau für immerwährende
Unterstützung.

iv Table of Contents
Danksagung iv
Abstract viii
List of Tables x
List of Figures xi
List of Schemes xiii
List of Abbreviations xiv

1 General Introduction 1
1.1 Carbon Allotropes and sp Carbon Chains 1
1.2 Research in the Gladysz Group 5
1.3 Aim of this Work 7
1.4 References 9
2 A Synthetic Breakthrough into an Unanticipated Stability Regime:
A Series of Isolable Complexes in which C , C , C , C , C , 6 8 10 12 16
C , C , and C Polyynediyl Chains Span Two Platinum Atoms 1420 24 28
2.1 Introduction 14
2.2 Results 15
2.2.1 Syntheses of Monoplatinum Complexes 15
2.2.2 Syntheses of Diplatinum Complexes 25
2.2.3 Crystallography and Cyclic Voltammetry 30
2.3 Discussion 40
2.3.1 Synthesis: Strategic Considerations 40
2.3.2 Thermal and Oxidative Stabilities 41
2.3.3 IR and NMR Spectra 42
2.3.4 UV-visible Spectra 44
2.3.5 Structures 47
v 2.3.6 Conclusions 48
2.4 Experimental 50
2.5 References 73
3. Longitudinally Extended Molecular Wires based upon Pt(C≡C) 4
Repeat Units; Iterative Syntheses of Functionalized Linear PtC Pt, 8
PtC PtCPt, and PtC PtC PtCPt Assemblies with Terminal 8 8 8 8 8
Chloride 78
3.1 Introduction 78
3.2 Results 81
3.2.1 Syntheses of Diplatinum Complexes 81
3.2.2 Syntheses of Tri- and Tetraplatinum Complexes 84
3.2.3 Other Chemistry 85
3.2.4 Characterization of Compounds 91
3.3 Discussion 96
3.3.1 Syntheses of Title Complexes 96
3.3.2 Thermal Stabilities 99
3.3.3 IR and NMR Spectra 99
3.3.4 UV-visible Spectra 100
3.3.5 Structures 102
3.3.6 Oxidative Stabilities 102
3.3.7 Conclusions 103
3.4 Experimental 104
3.5 References 115
4. Introduction of Terminal Sulfur Functionality into Longitudinally
Extended Molecular Wires based upon PtC Pt, PtC PtC Pt, and 8 8 8
PtC PtC PtC Pt Assemblies 1208 8 8
4.1 Introduction 120
vi 4.2 Results 120
4.2.1 Synthesis 120
4.2.2 Characterization of Compounds 122
4.3 Discusion 125
4.3.1 Syntheses of 41, 42, and 43 125
4.3.2 IR and NMR Spectra 125
4.3.3 UV-visible Spectra and Oxidative Stabilities 126
4.3.4 Structure of 40 and Conductivity for Complexes 41, 42 and 43 127
4.3.5 Conclusions 129
4.4 Experimental 130
4.5 References 135
5. Appendix 137
5.1 Crystallography 137
5.2 Diagrams of Relationships of Various NMR Properties to the Number
of C≡C Units 151
5.3 Compound Numbers 160
5.4 Zusammenfassung 162
Publikationsliste
Lebenslauf







vii Abstract

The reaction of trans-(p-tol)(p-tol P) PtCl (7) and H(C≡C) H (1) (cat. CuI, HNEt ) 3 2 2 2
gives trans-(p-tol)(p-tol P) Pt(C≡C) H (8, 82%), which couples with excess HC≡CSiEt 3 2 2 3
(acetone, O , CuCl/TMEDA; Hay conditions) to yield trans-(p-tol)(p-tol P) Pt(C≡C) SiEt 2 3 2 3 3
+ −(9, 77%). The addition of n-Bu N F in wet acetone to 9 gives trans-(p-tol)(p-4
−tol P) Pt(C≡C) H (10, 84%); the further addition of ClSiMe (F scavenger) and excess 3 2 3 3
HC≡CSiEt gives trans-(p-tol)(p-tol P) Pt(C≡C) SiEt (11, 23%). Similar Hay couplings of 3 3 2 4 3
trans-(p-tol)(p-tol P) PtC H (generated in situ analogously to 10 for x ≥ 8) and excess 3 2 x
H(C≡C) SiEt (3) yield (a) x = 4, 11 (29%), trans-(p-tol)(p-tol P) Pt(C≡C) SiEt (13, 30%), 2 3 3 2 6 3
and trans-(p-tol)(p-tol P) Pt(C≡C) SiEt (1%), (b) x = 6, trans-(p-tol)(p-3 2 8 3
tol P) Pt(C≡C) SiEt (12, 59%), and trans-(p-tol)(p-tol P) Pt(C≡C) SiEt (14, 7%), (c) x = 3 2 5 3 3 2 7 3
8, 13 (42%) and (d) x = 10, 14 (20%). Hay homocoupling of 8, 10, desilylated 11, and
desilylated 12 give trans,trans-(p-tol)(p-tol P) Pt(C≡C) Pt(Pp-tol ) (p-tol) (74%), 3 2 4 3 2
trans,trans-(p-tol)(p-tol P) Pt(C≡C) Pt(Pp-tol ) (p-tol) (20, 83%), trans,trans-(p-tol)(p-3 2 6 3 2
tol P) Pt(C≡C) Pt(Pp-tol ) (p-tol) (70%), and trans,trans-(p-tol)(p-tol P) Pt(C≡C) Pt(Pp-3 2 8 3 2 3 2 10
tol ) (p-tol) (72%), but trans-(p-tol)(p-tol P) Pt(C≡C) H decomposes too rapidly. However, 3 2 3 2 6
when 13 and 14 are subjected to Hay conditions, protodesilylation occurs in situ and
trans,trans-(p-tol)(p-tol P) Pt(C≡C) Pt(Pp-tol ) (p-tol) (36%) and trans,trans-(p-tol)(p-3 2 12 3 2
tol P) Pt(C≡C) Pt(Pp-tol ) (p-tol) (51%) are isolated. Reactions of desilylated 9 and 3 2 14 3 2
desilylated 12 with 7 (CuI, HNEt ) give trans,trans-(p-tol)(p-tol P) Pt(C≡C) Pt(Pp-tol ) (p-2 3 2 3 3 2
tol) (17, 56%) and trans,trans-(p-tol)(p-tol P) Pt(C≡C) Pt(Pp-tol ) (p-tol) (19, 84%). The 3 2 5 3 2
effect of the trans,trans-(p-tol)(p-tol P) PtC Pt(Pp-tol ) (p-tol) chain lengths upon thermal 3 2 x 3 2
stabilities (T ≥ 200 °C for x ≤ 16), IR ν patterns (progressively more bands), colors C≡C
(yellow to orange to deep red), UV-visible spectra (progressively red-shifted and intense
−1 −1bands with ε > 400000 M cm ), redox properties (progressively more difficult oxidations),
and NMR spectra (many monotonic trends) are analysed, including implications for the sp
carbon allotrope carbyne. The crystal structures of 9, 11, 12, 17, 19, and 20 are determined.
viii Reaction of cis-(p-tol P) PtCl (26) and Me Sn(C≡C) SiMe (25) (1:1, THF, reflux) 3 2 2 3 2 3
gives the monosubstituted product trans-Cl(p-tol P) Pt(C≡C) SiMe (30, 63%). Treatment 3 2 2 3
+ –with wet n-Bu N F yields trans-Cl(p-tol P) Pt(C≡C) H (96%), and Hay oxidative 4 3 2 2
homocoupling gives trans,trans-Cl(p-tol P) Pt(C≡C) Pt(Pp-tol ) Cl (32, 68%), the crystal 3 2 4 3 2
structure of which is determined. Reaction of 32 and 25 (1:1, RT) gives the monochloride
complex trans,trans-Cl(p-tol P) Pt(C≡C) Pt(Pp-tol ) (C≡C) SiMe (46%), which can be 3 2 4 3 2 2 3
converted by a similar desilylation/homocoupling sequence to trans,trans,trans,trans-Cl(p-
tol P) Pt(C≡C) Pt(Pp-tol ) (C≡C) (p-tol P) Pt(C≡C) Pt(Pp-tol ) Cl (36, 48%; 79% under 3 2 4 3 2 4 3 2 4 3 2
one-pot conditions). The condensation of 26 and excess H(C≡C) SiMe (2) (HNEt , cat. CuI) 2 3 2
gives trans-Me Si(C≡C) Pt(Pp-tol ) (C≡C) SiMe (27, 78%), which upon treatment with 3 2 3 2 2 3
+ –wet n-Bu N F affords trans-H(C≡C) Pt(Pp-tol ) (C≡C) H (96%). Hay oxidative cross 4 2 3 2 2
coupling with desilylated 30 in situ (1:4) gives trans,trans,trans-Cl(p-tol P) Pt(C≡C) Pt(Pp-3 2 4
tol ) (C≡C) Pt(Pp-tol ) Cl (35) in 36% yield after chromatography, together with 33% of the 3 2 4 3 2
homocoupling product 32. Reaction of 32 and 2 (1:5) gives surprisingly 27, not trans,trans-
Me Si(C≡C) (p-tol P) Pt(C≡C