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Complexes with Chelating Phosphine Ligands and Their Application in Catalytic Fluorination and Dioxygen Activation

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Complexes with Chelating Phosphine Ligands and Their Application in Catalytic Fluorination and Dioxygen Activation Research Collection Doctoral Thesis Five-coordinate ruthenium and osmium(II) complexes with chelating phosphine ligands and their application in catalytic fluorination and dioxygen activation Author(s): Bàrthàzy, Péter Tamàs Publication Date: 2000 Permanent Link: https://doi.org/10.3929/ethz-a-004044162 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Dissertation ETH Nr 13841 Five-Coordinate Ruthenium and Osmium(II) Complexes with Chelating Phosphine Ligands and their Application in Catalytic Fluorination and Dioxygen Activation A Dissertation Submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZUERICH For the degree of DOCTOR OF NATURAL SCIENCES Presented by Péter Tamàs Bàrthàzy, Dipl. Chem. born on January 21st, 1972 from Obersiggenthal (AG) Accepted on recommendation of Prof. Dr. A. Togni, Examiner Prof. Dr. A. Pfaltz, Co-examiner Dr. A. Mezzetti, Co-examiner Zürich, 2000 Danksagung Eine Doktorarbeit ist immer eine Koproduktion vieler Menschen, die ihren kleinen und gros¬ sen Beitrag zum Gelingen geleistet haben. Prof. Dr. Antonio Togni: Er hat daneben, dass er meine Arbeit betreut und beaufsichtigt hat, vor allem mir, der sich selber fuer einigermassen effizient hält, die wahre Bedeutung desselben Wortes beigebracht: Ohne grosse Instruktionen hat er doch den Gang meiner Arbeit entschei¬ dend beeinflusst. Dr. Antonio Mezzetti: Als mein eigentlicher Betreuer hat er durch konstantes Fordern ein¬ dafuer erseits, aber vor allem durch grosse chemische und menschliche Flexibilität andererseits gesorgt, dass es immer vorwärts ging und die Chemie immer stimmte. Prof. Dr. Andreas Pfaltz für die freundliche Uebernahme der Korreferates einerseits und für die Unterstützung während des Studiums andererseits. Dr. Michael Wörle und Dr. Heinz Rüegger: Ohne ihren Beitrag wäre die Dissertation viel trockener und kaum bebildert. und die Die ganzen Kollegen der Gruppe Togni, denen ich für das gute Arbeitsklima produk¬ tive Zusammenarbeit sehr dankbar bin: Andrea, Céline, Christoph, Diego, Francesca, Giorgio, Hami, Ivo, Lukas, Markus, Nik, Pascal, Patrick, Raoul, Rhony, Robert, Romano, Stan, Stefan Z., Terrance und all den temporären Gruppenmitgliedern. Zwei gehören hervorgehoben: Stephan B. und Maya F., die, hmm, immer die richtige Antenne für mich hatten? Meinen Eltern und meiner Schwester Eszter, die mich während meiner gesamten Ausbildungs¬ zeit unterstützt haben, auch wenn es nicht immer leicht war. Last, but definitively not least meiner Freundin Fabia, die gerade durch ihre unsichtbare, dafür hatte. umso stetere Unterstützung sicher einen der schwereren Aufgaben auf sich genommen Vielen Dank für alles, Qu... Publications Parts of this dissertation have been published: • Dioxygen Activation at [OsCl(dcpe)2]+ Gives [OsCl(0)(dcpe)2]+, the First Stable Oxo Complex of Osmium (IV) Barthazy, P.; Wörle, M.; Mezzetti, A. /. Am. Chem. Soc. 1999,121, 480. • Carbon-Fluorine Bond Formation via a Five-Coordinate Fluoro Complex OfRuthenium (II) Barthazy, P.; Hintermann, L.; Stoop, R. M.; Wörle, M.; Mezzetti, A.; Togni, A. Helv. Chim. Acta 1999, 82, 2448. • Towards Metal-Mediated C-F Bond Formation. Synthesis and Reactivity of the 16- Electron Fluoro Complex [RuF(dppp)2]PF6 Barthazy, P.; Stoop, R. M.; Wörle, M.; Mezzetti, A.; Togni, A. Organometallics, 2000, 19, 2844. • Oxo Complexes ofOsmium(IV) by Dioxygen Activation. X-ray Structures of [OsX(dcpe)2]PF6 (X=Cl, Br), [OsCl(î]2-02(dcpe)2]BPh4 and [OsCl(0)(dcpe)2]BPh4 Barthazy, P.; Wörle, M.; Riiegger, H.; Mezzetti, A . Inorganic Chemistry, 2000, 59,4903. • Catalytic Fluorination by Halide Metathesis with 16-Electron Ru(II) Complexes. X- ray Structure of [Tl(ß-F)2Ru(dppe)2]PF6. Barthazy, P.; Mezzetti, A.; Togni, A.; in preparation. • Making a 16-electron bromo (or iodo) complex ofruthenium(H) and a C-F bond in one pot Barthazy, P.; Broggini, D.; Mezzetti, A.; submitted to Can. J. Chem Abstract The first part of this work shows a new application of five-coordinate ruthenium(II) complexes with chelating ligands in fluorination reactions. Organic halides such as chlorides and bromides can be converted to the corresponding fluorides in a nucleophilic substitution with fluoride. The uncatalyzed reaction only works well with greatly activated organic halides such as Ph3CCl and a strong halide scavenger such as AgF or TIF. We now find that complexes of the type [RuF(P-P)2]+ or [RuCl(PNNP)]+ are able to catalyze such reactions and to broaden the scope of potential substrates. K CIN= 0-p/6'p =K ÇJ,N=\ ^-? Ph2 \=/ Pho Ph2 Ph2x=/ [RuCI2(DAC)] [RuCI2(redDAC)] [RuCI2(BPA)] [RuCI2(BNA)] [RuF(dppp)2r [RuCI(dppe)2]+ (S-S)-[RuCI(chiraphos)2]+ For the catalyzed reaction only a moderately activated substrate is required such as a tertiary halide of any kind or a secondary carbon atom with one phenyl substituent. Complete conversion can be achieved within one day with 1 mol% of the catalyst, PhMeCHBr as sub¬ strate, and TIF as source of fluoride, whereas the blank reaction produces less than 1% of the corresponding fluoride. The yield of PhMeCHF in the catalytic reaction is up to 76% as con¬ firmed via GC analysis and NMR spectroscopy. 1-10 mol% Cata'ySt + T,F ^^ +TICI , RT, CH2CI2 One of the P-P and all of the PNNP ligands used are chiral and therefore enantiomer- ically pure complexes were tested in catalysis. In the case of PNNP = DAC an enantiomeric excess of 13% at 4% conversion was measured, which drops to 3% at full conversion. This result indicates a kinetic resolution of the racemic starting material. The fact that the ee does not drop to 0% can be explained either by the formation of byproducts, which are differently favored in the case of the two enantiomers, or by a slight enantiodiscrimination (face selectiv¬ ity of the free carbocation). The second part of the work deals with the coordination of dioxygen at coordinatively unsaturated 16 electron-complexes of Os(II) of the type [Os(X)(02)(P-P)2]+ with X = CI, Br and with the reduction to the Os(IV) oxo complexes [Os(X)(0)(P-P)2]+. With X = CI and P-P = dcpe all members of the series n = 0, 1 and 2 of [Os(X)(0)n(P-P)2]+ were isolated and fully characterized, including all three crystal structures. Both the dioxygen and the oxo complexes turned out to be surprisingly unreactive, and no productive oxygen transfer could be developed. For all tested substrates, a well-behaved reaction was obtained only with PPh3 and iodide as reducing agent, but with standard organic substrates no reaction could be induced. + + Cy Cy | CX Cy I O Vo-0... 1 ... _V cvi ^p^Cy Np /èy P^ I P 'Cy CI / C. \ / \ Cy Cy °y Cy + + Cy Cy | Cy Cy | + 0=PPh3 VP-Cy /[ s NPP 'Cy P-Uy ipP 'CyCy ^P^CyP^Cy | CI / CI \ / \ Cy Cy Cy Cy However, these complexes are interesting from a theoretical point of view as they are homologous to postulated intermediates of some catalytic cycles, such as the natural process of dioxygen activation with the heme moiety or the epoxidation of olefines with [RuCl(PNNP)]+. Both these systems have a number of features in common with the osmium complexes, that is the electron configuration of the metal, as well as the formal electron count of the complex and the main structure of the ligand set. In all cases the metal belongs to the iron triad and is either +2 for the oxygen-free complex or +4 for the oxo complex. The metal center is surrounded by four chelating neutral donor atoms from group V (N or P), which like to adopt a planar geome¬ try and an anionic halide ligand occupies the coordination site trans to the reactive site. Zusammenfassung Der erste Teil dieser Arbeit zeigt eine neue Anwendung der ansonsten wohlbekannten fünffach koordinierten Ruthenium(II) Komplexe mit mehrzähnigen Liganden als Fluori- dierungskatalysatoren. Organische Halogenide wie beispielsweise Chloride oder Bromide können in einer nukleophilen Substitution zu den entsprechenden Fluoriden umgesetzt werden. Diese unkatalysierte Reaktion ist nur mit stark aktivierten Halogeniden wie zum Beispiel Ph3CCl, und einem Halogenid bindendem Fluorierungsmittel wie AgF oder TIF sinnvoll durchführbar. Wir haben beobachtet, dass Komplexe des Typs [RuF(P-P)2]+ oder [RuCl2(PNNP)] in der Lage sind, solche Reaktionen zu katalysieren und den Bereich der brauchbaren Substrate zu erweitern. /=N. ÇlN=\ /A>p^T\ rr-L Ruf V-, ^-? \=/ C»^J Ph2 Ph2ph2\=/ Pn2 ph2\=/ x^r? Phc rw^JTs \=/ Php Phh2\=/ [RuCI2(DAC)] [RuCI2(redDAC)] [RuCI2(BPA)] [RuCI2(BNA)] [RuF(dppp)2r [RuCI(dppe)2]+ (S-S)-[RuCI(chiraphos)2]+ Für die katalysierte Reaktion ist nunmehr nur noch ein massig aktiviertes Substrat vonnöten wie zum Beispiel ein tertiäres Halogenid oder ein sekundäres mit einem Phenylsub- stituenten. Mit 1 mol-% Katalysator, PhMeCHBr als Substrat und TIF als Fluoridquelle erfolgt quantitativer Umsatz innerhalb eines Tages, wobei die unkatalysierte Reaktion weniger als 1% Umsatz zeigt. Die Ausbeute beträgt gemäss NMR-Spektroskopie und GC-Analyse bis zu 76%. 1-10 mol% catalyst ^ ^ + TIF ^5^\ +TICI » RT, CH2CI2 Einer der verwendeten P-P und alle PNNP-Liganden sind chiral und somit wurden chirale Komplexe in der Katalyse verwendet. Für den Liganden PNNP = DAC wurde ein Enan- tiomerenüberschuss von 13% bei 4% Umsatz erhalten, welcher auf 3% bei voUsändigem Umsatz fiel. Dieser Reaktionsverlauf ist ein Indiz für kinetische Racematspaltung des Eduktes. Die Tatsache, das der Enantiomerenüberschuss im Produkt nicht auf 0% fällt, wie von der The¬ orie eigentlich verlangt, kann entweder mit der Bildung von Nebenprodukten erklärt werden, die nicht für beide Enantiomere gleich günstig ist oder alternativ mir einer leichten Enantiodis- kriminierung durch das freie Carbokation. Der zweite Teil der Arbeit handelt von der Koordination von Disauerstoff an koordi- nativ ungesättigte 16 e~-Komplexe von Os(II) des Typs [Os(X)(02)(P-P)2]+ mit X = Cl, Br und von deren Umwandlung in die Os(IV) Oxokomplexe [Os(X)(0)(P-P)2]+.
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