New approaches to catalytic C-H and C-C bond cleavage with ruthenium complexes [Elektronische Ressource] / vorgelegt von Daniela Giunta

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Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2004
• Nombre de lectures: 8
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

New Approaches to Catalytic C-H and
C-C Bond Cleavage with Ruthenium
Complexes
Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der Rheinisch-Westfälischen Technischen Hochschule Aachen zur Erlangung des
akademischen Grades einer Doktorin der Naturwissenschaften genehmigte Dissertation
vorgelegt von
Diplom-Chemikerin
Daniela Giunta
aus Sassari
Berichter: Universitätsprofessor Dr. Walter Leitner
Universitätsprofessor Dr. Jun Okuda
Tag der mündlichen Prüfung: 18. Juni 2004
Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.The experimental part of the work has been carried out in the period between November
2000 to June 2002 in the Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr
and between July 2002 to August 2003 in the Institut für Technische und Makromolekulare
Chemie RWTH-Aachen, in the reasearch group of Prof. Dr. Walter Leitner.
I wish to thank Professor Dr. Walter Leitner for the opportunity to work in his group,
his interest, and enthusiasm in the helpful discussions about the scientific and more technical
problems. I also would like to thank him for supporting my active participation to many
international scientific meetings and conferences.
I would like to thank the former director of the "Max-Planck-Institut für
Kohlenforschung", Prof. Dr. Manfred T. Reetz for giving me the opportunity to work in a
such excellent and historical institute.
Furthermore, I am grateful to Professor Dr. Jun Okuda for accepting to be the second
referee for this thesis (Korreferent).Table of Contents
1 General Introduction ..................................................................................................... 6
1.1 Catalysis with Well-Defined Organometallic Compounds........................................... 7
1.2 Metal-Carbenes ............................................................................................................. 9
1.3 Background and Aim of This Thesis........................................................................... 15
1.3.1 Synthesis of novel non-classical hydrides ruthenium-carbene complexes ................. 15
1.3.2 Reactivity and catalytic applications of novel ruthenium-carbene complexes ........... 16
1.3.3 New solvents for ring-closing olefin metathesis......................................................... 17
1.4 References ...................................................................................................................19
2 Novel Non-Classical Hydride Ruthenium Complexes Containing Carbene Ligands. 22
2.1 N-Heterocyclic Carbenes as Ligands for Catalysis..................................................... 23
2.1.1 Main electronic and structural features of N-heterocyclic carbene ligands ................ 23
2.1.2 Reactivity and catalytic applications of NHC ligands ................................................ 25
2.2 Non-Classical Hydrides Complexes............................................................................ 32
2.2.1 Structure and bonding of non-classical hydride ligands ............................................. 32
2.2.2 Reactivity of non-classical hydride metal complexes ................................................. 40
2.3 Synthesis and Characterization of New Non-Classical Hydride Ruthenium Complexes
Containing N-Heterocyclic Carbene Ligands. ............................................................ 42
2.3.1 Background .................................................................................................................42
2.3.2 Synthesis of the complexes [(IMes) Ru(H) (H ) (PCy ) ] ....................................... 43x 2 2 2 3 2-x
2.3.3 Characterization of the complexes [(IMes) Ru(H) (H ) (PCy ) ]............................ 49x 2 2 2 3 2-x
2.4 Summary ..................................................................................................................... 59
2.5 Experimental ............................................................................................................... 63
2.5.1 General procedures...................................................................................................... 63
32.5.2 Synthesis of the 1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene........................... 63
2.5.3 Synthesis of the complex [(IMes)Ru(H) (H ) (PCy )] ............................................... 642 2 2 3
2.5.4plex [(IMes) Ru(H) (H ) ]......................................................... 642 2 2 2
2.5.5 Synthesis of the complex [Ag(IMes) ][AgCl ] ........................................................... 652 2
2.6 References ...................................................................................................................66
3 Catalytic Activity of the Complex [(IMes)Ru(H ) (H) (PCy )] ................................. 722 2 2 3
3.1 Background ................................................................................................................. 73
3.2 Catalytic H/D Exchange Processes ............................................................................. 74
3.3 Murai Reaction............................................................................................................ 84
3.4 Hydrogenation............................................................................................................. 88
3.4.1 Hydrogenation of ketones and aromatic rings............................................................. 89
3.4.2 Hydrogenation of nitriles ............................................................................................ 92
3.5 Summary ..................................................................................................................... 96
3.6 Experimental ............................................................................................................... 98
3.6.1 General procedures...................................................................................................... 98
3.6.2 Stoichiometric H/D-exchange experiments ................................................................ 98
3.6.3 Catalytic H/D-exchange experiments.......................................................................... 99
3.6.4 Murai reaction on aromatic ketone derivatives........................................................... 99
3.6.5 General procedure for the hydrogenation of anthracene............................................. 99
3.6.6 General procedure for the hydrogenation of adiponitrile.......................................... 100
3.7 References ................................................................................................................. 101
4 Metathesis in Ionic Liquids....................................................................................... 104
4.1 General Aspects of the Metathesis Reaction............................................................. 105
4.2 Catalysis in Ionic Liquids.......................................................................................... 110
4.3 Ring-Closing Metathesis in Ionic Liquids ................................................................ 114
44.3.1 Background ............................................................................................................... 114
4.3.2 Results and discussion............................................................................................... 115
4.4 Summary ................................................................................................................... 120
4.5 Experimental ............................................................................................................. 121
4.5.1 General techniques and materials.............................................................................. 121
4.5.2 RCM of 1,7-octadiene catalyzed by [RuCl (=CHPh)(PCy ) ] in absence of solvent1222 3 2
4.5.3 RCM of 1,7 octadiene catalyzed by [RuCl ) ] in [emim][Tf N] ...... 1222 3 2 2
4.5.4 (=CHPh)(PCy ) ] in [emim][Tf N] and2 3 2 2
extraction with pentane ............................................................................................. 123
4.5.5 RCM of 1,7-octadiene catalyzed by [RuCl (=CHPh)(PCy ) ] 5 in [emim][Tf N] and2 3 2 2
extraction with scCO ................................................................................................ 1232
4.6 References ................................................................................................................. 124
5 Summary and Outlook .............................................................................................. 127
Appendix A ........................................................................................................................... 134
A1 Crystal data and structure refinement for [(IMes)Ru(H) (H ) (PCy )]..................... 1352 2 2 3
A2 Crystal data and structure refineme) Ru(H) (H )(N )]......................... 1412 2 2 2
A3 Crystal data and structure refinement for [(IMes) Ru(H) (H ) ] .............................. 1442 2 2 2
6 Publications and Conference Proceedings ................................................................ 149
7 Curriculum Vitae....................................................................................................... 151
51 General Introduction
6General Introduction
1.1 Catalysis with Well-Defined Organometallic Compounds
A catalyst is widely