Tris(trimethylsilyl)silyl substituted alkali- and transition metal guaiazulenides [Elektronische Ressource] / by Yun Xiong

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2004
• Nombre de lectures: 22
• Langue: English
• Poids de l'ouvrage: 2 Mo

Extrait

1

Tris(trimethylsilyl)silyl Substituted Alkali-
and Transition Metal Guaiazulenides



Dissertation

Submitted in Partial Fulfilment of the Requirements for the Degree of
Doctor of Natural Science
-Dr.rer.nat.-

In the Institute of Inorganic and Analytical Chemistry

Department of Chemistry and Pharmacy

at

Johannes Gutenberg - University of Mainz


by

Yun Xiong

from P. R. China





Mainz 2004



I
1 INTRODUCTION ........................................................................................................................................ 1
1.1 ALKALI METAL HYPERSILANIDES............................................................................................................... 1
1.2 COORDINATION CHEMISTRY OF AZULENE SYSTEM ...................................................................................... 4
2 RESEARCH PROCESS.............. 14
2.1 THEORETICAL ANALYSIS........................................................................................................................... 14
2.2 MONO-HYP SUBSTITUTED ALKALIMETAL GUAIAZULENIDES...................................................................... 17
2.2.1 Addition ......................................................................................................................................... 17
2.2.1.1 Addition of Lithium Hypersilanide to Guaiazulene....................................................................................17
2.2.1.2 Addition of Potassium Hypersilanide to Guaiazulene................................................................................17
2.2.1.3 Addition of Cesium Hypersilanide to Guaiazulene19
2.2.2 NMR Spectroscopy......... 21
12.2.2.1 H NMR Spectroscopy...............................................................................................................................21
132.2.2.2 C NMR Spectroscopy26
292.2.2.3 Si NMR Spectroscopy..............................................................................................................................27
72.2.2.4 Li NMR Spectroscopy28
2.2.3 Molecular Structures of Compounds 1 and 2a .............................................................................. 29
2.2.3.1 Molecular Structure of [Li(6-Hyp-Hgual)] (1) .........................................................................................29 2
2.2.3.2 Molecular Structure of (thf) ⋅ K(6-Hyp-Hgual) (2a)..................................................................................33 4
2.3 MONO-HYP SUBSTITUTED METALLOCENE DERIVATIVES .......................................................................... 35
2.3.1 Reactions ...................................................................................................................................... 35
2.3.1.1 Metathesis of M(6-Hyp-Hgual) (M=Li, K) with MnBr , FeCl .................................................................35 2 2
2.3.1.2 Metathesis of K(8-Hyp-Hgual) with FeCl ................................................................................................37 2
2.3.1.3 Reaction of K(6-Hyp-Hgual) with NiCl or other Metal Halides..............................................................37 2
2.3.2 NMR Spectroscopy ....................................................................................................................... 39
2.3.2.1 NMR Spectra of Fe(6-Hyp-Hgual) (6) and Fe(8-Hyp-Hgual) (7) ...........................................................39 2 2
12.3.2.1.1 H NMR Spectroscopy.........................................................................................................................40
132.3.2.1.2 C NMctroscopy...........42
292.3.2.1.3 Si NMR Spectroscopy............................................................................................................43
2.3.2.2 NMR Spectroscopy of (3-Hyp-6-Hgua) (9)...............................................................................................43 2
12.3.2.2.1 H NMR Spectroscopy............43
132.3.2.2.2 C NMctroscopy...........46
292.3.2.2.3 Si NMR Spectroscopy...........47
2.3.3 Molecular Structures of Compounds 5, 6, 7, 8, and 9 .................................................................. 47
2.3.3.1 Molecular Structures of (RR)- and (SS)-M(6-Hyp-Hgual) (M=Mn 5, Fe 6, and Ni 8) ..........................47 2
2.3.3.2 Molecular Structure of Fe(8-Hyp-Hgual) (7)............................................................................................55 2
2.3.3.3 Conformation Analysis of (R,S)-Fe(6-Hyp-Hgual) (6) and (R,S)-Fe(8-Hyp-Hgual) (7)59 2 2
2.3.3.4 Molecular Structure of (3-Hyp-6-Hgual) (9)60 2
2.4 MONO-HYP SUBSTITUTED METALLOCENE DICHLORIDE DERIVATIVES...................................................... 62
2.4.1 Reactions ....................................................................................................................................... 62
2.4.1.1 Reaction of TiCl with K(6-Hyp-Hgual)(2) ................................................................................................62 3
2.4.1.2 Reactions of MCl (M=Zr(IV), Hf(IV)) with K(6-Hyp-Hgual) (2)..............................................................63 4
2.4.1.3 Reaction of ZrCp*Cl with K(6-Hyp-Hgual).............................................................................................64 3
2.4.2 NMR Spectroscopy ........................................................................................................................ 64
12.4.2.1 H NMR Spectroscopy...............................................................................................................................64
132.4.2.2 C NMR Spectroscopy67
292.4.2.3 Si NMR Spectroscopy..............................................................................................................................67
2.4.3 Molecular Structures of 10, 11 and 12 ..........................................................................................68
2.5 BIS-HYP SUBSTITUTED LITHIUM GUAIAZULENIDE .................................................................................... 73
2.5.1 Bis-Hyp Substituted Guaiazulene ................................................................................................. 73
2.5.1.1 Reaction......................73
2.5.1.2 NMR Spectroscopy......74
12.5.1.2.1 H NMR Spectroscopy ........................................................................................................................74
132.5.1.2.2 C NMR Spectroscopy77
292.5.1.2.3 Si NMR Spectroscopy.......................................................................................................................77
2.5.1.3 Molecular structure of 2,6-bis(Hyp)-H gua (14) .......................................................................................78 2
2.5.2 Bis-Hyp Substituted Lithium Guaiazulenide.................................................................................. 79
2.5.2.1 Reaction .....................................................................................................................................................79
2.5.2.2 NMR Spectroscopy......81
12.5.2.2.1 H NMR Spectroscopy...........81
132.5.2.2.2 C NMR Spectroscopy81
292.5.2.2.3 Si NMR Spectroscopy...........82
72.4.2.2.4 Li NMR Spectroscopy............83
2.5.2.3 Molecular Structure of [Li(2,6-bis(Hyp)-Hgual)] (15).............................................................................83 2
II
3 EXPERIMENT SECTION ........................................................................................................................ 87
3.1 GENERAL COMMENTS ............................................................................................................................. 87
3.2 CHARACTERIZATION................................................................................................................................87
3.2.1 Element Analysis............................................................................................................................ 87
3.2.2 Melting Point................................................................................................................................. 87
3.2.3 NMR-Spectroscopy......... 87
3.2.4 X-ray diffraction analysis .............................................................................................................. 88
3.3 SYNTHESIS AND CHARACTERIZATION........................................................................................................ 88
3.3.1 Syntheses of Reactants................................................................................................................... 88
3.3.1.1 Synthesis of Si(SiMe )88 3 4
3.3.1.2 Synthesis of KSi(SiMe ) ............................................................................................................................89 3 3
3.3.1.3 Synthesis of LiSi(SiMe )90 3 3
3.3.1.4 Synthesis of CsSi(SiMe ) ...........................................................................................................................91 3 3
3.3.2 Syntheses and Characterization of New Compounds .................................................................... 91
3.3.2.1 [Li(6-Hyp-Hgual)] (1) .................................................................................