&amp / #945 / ,&amp / #946 / -Unsaturated cyclic ketones were selectively oxidized on &amp / #945 / &#039 / - positions using Mn(OAc)3 and Pb(OAc)4, respectively. The resultant racemic &amp / #945 / &#039 / -acetoxylated substrates were resolved into corresponding enantiomerically enriched &amp / #945 / &#039 / -hydroxylated and &amp / #945 / &#039 / -acetoxylated compounds via PLE hydrolysis. &amp / #945 / &#039 / -Hydroxylated compounds are racemized quickly, so they were acetylated with acetyl chloride and pyridine in situ to give the corresponding &amp / #945 / &#039 / -acetoxylated compounds. Resultant &amp / #945 / &#039 / -acetoxy &amp / #945 / ,&amp / #946 / -unsaturated cyclic ketones reacted with excess amount of diazomethane under the catalsts of Pd(OAc)2 to give the resulting bicyclic diastereomeric products. At the end of the experiment, Enantiomeically enriched 2-oxobicyclo[3.1.0]hexan-3-yl acetate and 2-oxobicyclo[4.1.0]heptan-3-yl acetate were chemoenzymatically synthesized.

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Agradecemos a compreensão. on 2016-04-05T16:11:36Z (GMT) / Submitted by THALES REGGIANI DE MOURA null (thales4014@gmail.com) on 2016-04-05T16:36:02Z No. of bitstreams: 1 Dissertação - Thales v.4 final.pdf: 4604603 bytes, checksum: 672981e0a2bf60064cd38703b98325bf (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-04-05T17:25:38Z (GMT) No. of bitstreams: 1 moura_tr_me_araiq.pdf: 4604603 bytes, checksum: 672981e0a2bf60064cd38703b98325bf (MD5) / Made available in DSpace on 2016-04-05T17:25:38Z (GMT). No. of bitstreams: 1 moura_tr_me_araiq.pdf: 4604603 bytes, checksum: 672981e0a2bf60064cd38703b98325bf (MD5) Previous issue date: 2016-03-09 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nos últimos anos, o interesse na obtenção de novos fármacos à base de metais visando o tratamento de cânceres vem aumentando consideravelmente. A descoberta da atividade antitumoral da cisplatina e seu subsequente sucesso como fármaco no tratamento do câncer inspirou o estudo de inúmeros complexos análogos, que apresentaram, em geral, padrões similares de atividade antitumoral e susceptibilidade à resistência. Por apresentarem mesmas configuração eletrônica e geometria em relação à compostos de Pt(II), compostos de coordenação contendo o íon Pd(II) foram amplamente estudados, sendo reconhecido para os compostos de Pd(II) contendo ligantes N,S-doadores, modos de ação distintos em relação ao compostos de Pt(II). Neste trabalho foram sintetizados e caracterizados 4 novos complexos de paládio(II) do tipo [PdX(tedmPz’)(PPh3)] {tedmPz’ = N-etil-1-iminotiolato-3,5-dimetilpirazol; X = Cl-, Br-, I-, SCN-; PPh3 = trifenilfosfina}. Os complexos foram caracterizados pelas técnicas de espectroscopia vibracional na região do IV e RMN de 1H e 13C, análise elementar, espectrometria de massas ESI/MS e difração de raios X de monocristal, indicando um ambiente quadrático plano ao redor do metal, com seus sítios de coordenação ocupados pela trifenilfosfina, e pelo ligante tedmPz coordenado de maneira N,S-aniônica e ligante tiocianato ligado de modo N-terminal. Também é descrita a síntese e caracterização espectroscópica na região do IV e RMN de 1H e 13C do ligante tedmPz. A citotoxicidade in vitro do ligante e de todos os complexos foi avaliada pelo método do MTT, frente as culturas celulares de tumores murinos MCF-7 (adenocarcinoma mamário humano). Todos os compostos tiveram sua capacidade de interação com um nucleosídeo (guanosina) investigada com o objetivo de avaliar sua possível interação covalente com o DNA. Os resultados obtidos indicaram que a variação dos ligantes haletos não interferiu na citotoxicidade dos complexos, bem como os compostos sintetizados não apresentaram capacidade de interagir com a guanosina, sendo esta uma evidência preliminar de que a interação covalente entre os compostos sintetizados e a guanina presente no DNA não é o mecanismo de citotoxicidade destes. Vale destacar que todos os compostos foram mais citotóxicos que a cisplatina, obtendo-se em média valores de IC50 de até 2,4 vezes menor que o fármaco de comparação. / In the last years, the interest of new drugs based on metals in order to treat cancers has been increasing considerably. The discovery of cisplatin antitumor activity and its subsequent success as a cancer treatment drug has inspired the study of several analogous compounds, which presented, in general, similar patterns of antitumor activity and susceptibility to resistance. By presenting the same electronic configuration and geometry of Pt(II) complexes, coordination complex containing Pd (II) ion have been extensively studied, and recognized different activity patterns for these compounds containing ligands N,S-donor in relation to compounds of Pt (II). In this work, were synthesized and characterized four novel complexes of palladium(II) type [PdX(tedmPz')(PPh3)] {tedmPz' = N-ethyl-1-iminothiolate-3,5-dimethylpyrazole; X = Cl-, Br-, I-, SCN-; PPh3 = triphenylphosphine}. The complexes were characterized by vibrational spectroscopy techniques in the IV region and 1H NMR and 13C NMR, elemental analysis, mass spectrometry ESI / MS and X-ray diffraction of single crystal, indicating a square planar environment around the metal with its sites coordination occupied by triphenylphosphine, the N,S-anionic coordination of tedmPz ligand, the N-terminal coordination mode of thiocyanate. It is also described the synthesis and spectroscopic characterization in the IV region and 1H NMR and 13C for the tedmPz compound. The in vitro cytotoxicity of the ligand and all of the complexes were evaluated by the MTT method, against the cell cultures of murine tumors MCF-7 (human breast adenocarcinoma). All compounds had their ability to interact with a nucleoside (guanosine) investigated with the objective of evaluating their possible covalent interaction with DNA. The results indicated that the variation of halide ligands did not affect the cytotoxicity of the complexes and the synthesized compounds showed no ability to interact with guanosine, which is a preliminary evidence that covalent interaction between the synthesized compounds and the DNA is not the main source of cytotoxicity of these. It is noteworthy that all the compounds were more cytotoxic than cisplatin, obtaining an average of IC50 values of up to 2.4 times lower than the comparison drug. / CNPq: 132644/2014-2

Les interactions entre des complexes de platine (II) ou de palladium (II) ont une grande influence sur une grande gamme de propriétés chimiques et physiques. Ces propriétés peuvent être étudiées par plusieurs méthodes spectroscopiques comme la spectroscopie Raman, d’absorption, d’émission et de réflectivité diffuse. L’empilement de molécules a un effet important sur les propriétés spectroscopiques de plusieurs composés des éléments de transition. La spectroscopie est très utile pour comprendre les effets intermoléculaires majeurs de plusieurs composés inorganiques. Les complexes plan-carré de platine(II) et de palladium(II) sont très intéressants à cause de leur grande quantité d’effets intermoléculaires et intramoléculaires. Des mesures avec des variations de pression (entre 1 bar et 40 kbar) et de température (entre 80 K et 300 K) ont été effectuées sur ces complexes. La structure à l’état fondamental des composés de platine(II) et de palladium(II) a un effet important sur la spectroscopie de luminescence. Des complexes avec des donneurs axiaux mènent à un effet de déplacement du maximum d’émission vers de plus basses énergies avec l’augmentation de pression. Des complexes similaires sans composante axiale ont un maximum d’émission qui se déplace vers des plus hautes énergies. Ces effets sont explorés à l’aide de plusieurs composés incluant une série de complexes pinceur qui ont démontré des déplacements entre -1 cm-1/kbar et -30 cm-1/kbar. Le changement du type d’émission causé par un changement de pression ou de température est aussi observable. Un complexe de platine(II) montre un changement d’une transition centrée sur le ligand à pression ambiante à une transition de type transfert de charge à plus haute pression. La combinaison de l’information cristallographique et spectroscopique donne de l’information quantitative sur les variations de la structure et des niveaux électroniques de plusieurs complexes. / Interactions between platinum(II) or palladium (II) compounds influence a large range of chemical and materials properties. These properties can be studied with the help of many different spectroscopic methods such as Raman, absorption, luminescence and diffuse reflectance. The stacking of molecules has a very important effect on their photophysical properties. Luminescence spectroscopy is especially useful to understand what role of intermolecular effects in inorganic complexes. Square planar Pt(II) and Pd(II) complexes are very interesting to study because of their multiple intermolecular and intramolecular effects. Work on these complexes under variable external pressure and temperature corresponding to variable intermolecular effects was executed. These changes include variations of pressure (between ambient pressure and 40 kbar) and temperature (from 80 K to 300 K). The ground-state structure of Pt(II) and Pd(II) square planar complexes has an obvious impact on the luminescence properties. Pressure allows a continuous variation of the structure. Complexes with axial donors show a shift of the luminescence maxima to lower energy as pressure increases, similar complexes without the axial component show a shift of the luminescence maxima to higher energy. The packing also plays an important role defining effects of pressure and temperature. These effects are illustrated with a series of pincer complexes that have shown energy shifts between -1 cm-1/kbar and -30 cm-1/kbar. These complexes also show different emitting states depending on the pressure that is applied. A ligand centered (LC) transition is observed at low pressure replaced by a metal-ligand charge transfer (MLCT) emission at higher pressure. The combination of crystallographic and spectroscopic data gives quantitative variations of the electronic structure for many complexes.

Les interactions entre des complexes de platine (II) ou de palladium (II) ont une grande influence sur une grande gamme de propriétés chimiques et physiques. Ces propriétés peuvent être étudiées par plusieurs méthodes spectroscopiques comme la spectroscopie Raman, d’absorption, d’émission et de réflectivité diffuse. L’empilement de molécules a un effet important sur les propriétés spectroscopiques de plusieurs composés des éléments de transition. La spectroscopie est très utile pour comprendre les effets intermoléculaires majeurs de plusieurs composés inorganiques. Les complexes plan-carré de platine(II) et de palladium(II) sont très intéressants à cause de leur grande quantité d’effets intermoléculaires et intramoléculaires. Des mesures avec des variations de pression (entre 1 bar et 40 kbar) et de température (entre 80 K et 300 K) ont été effectuées sur ces complexes. La structure à l’état fondamental des composés de platine(II) et de palladium(II) a un effet important sur la spectroscopie de luminescence. Des complexes avec des donneurs axiaux mènent à un effet de déplacement du maximum d’émission vers de plus basses énergies avec l’augmentation de pression. Des complexes similaires sans composante axiale ont un maximum d’émission qui se déplace vers des plus hautes énergies. Ces effets sont explorés à l’aide de plusieurs composés incluant une série de complexes pinceur qui ont démontré des déplacements entre -1 cm-1/kbar et -30 cm-1/kbar. Le changement du type d’émission causé par un changement de pression ou de température est aussi observable. Un complexe de platine(II) montre un changement d’une transition centrée sur le ligand à pression ambiante à une transition de type transfert de charge à plus haute pression. La combinaison de l’information cristallographique et spectroscopique donne de l’information quantitative sur les variations de la structure et des niveaux électroniques de plusieurs complexes. / Interactions between platinum(II) or palladium (II) compounds influence a large range of chemical and materials properties. These properties can be studied with the help of many different spectroscopic methods such as Raman, absorption, luminescence and diffuse reflectance. The stacking of molecules has a very important effect on their photophysical properties. Luminescence spectroscopy is especially useful to understand what role of intermolecular effects in inorganic complexes. Square planar Pt(II) and Pd(II) complexes are very interesting to study because of their multiple intermolecular and intramolecular effects. Work on these complexes under variable external pressure and temperature corresponding to variable intermolecular effects was executed. These changes include variations of pressure (between ambient pressure and 40 kbar) and temperature (from 80 K to 300 K). The ground-state structure of Pt(II) and Pd(II) square planar complexes has an obvious impact on the luminescence properties. Pressure allows a continuous variation of the structure. Complexes with axial donors show a shift of the luminescence maxima to lower energy as pressure increases, similar complexes without the axial component show a shift of the luminescence maxima to higher energy. The packing also plays an important role defining effects of pressure and temperature. These effects are illustrated with a series of pincer complexes that have shown energy shifts between -1 cm-1/kbar and -30 cm-1/kbar. These complexes also show different emitting states depending on the pressure that is applied. A ligand centered (LC) transition is observed at low pressure replaced by a metal-ligand charge transfer (MLCT) emission at higher pressure. The combination of crystallographic and spectroscopic data gives quantitative variations of the electronic structure for many complexes.

Im ersten Teil der Arbeit wird die Synthese neopentyl- und neosilylsubstituierter Phosphane zur Verwendung als Liganden in katalytisch aktiven Palladiumkomplexen beschrieben. Die Aktivität wurde in der Suzuki-Miyaura Kreuzkupplungsreaktion getestet. Während die neosilylsubstituierten Phosphane 2:1 Addukte (5b und 5d) mit geeigneten Palladiumsalzen bilden, welche moderate Katalyseaktivität zeigen, untergehen die neopentylsubstituierten Komplexe schnelle Cyclometalierungsreaktionen in Gegenwart von Basen und bilden die katalytisch wenig aktiven Palladacyclen (6a, 6e, and 6g). Die deaktivierende Cylometallierung konnte durch Darstellung der Palladiumcomplexe ausgehend von Pd(cod)Cl2 in Abwesenheit von Basen vermieden werden. Die erhaltenen 2:1 Phosphaneaddukte zeigten deutlich verbesserte Aktivität. Daraus wurde geschlossen, dass die Cyclomettalierung als Nebenreaktion eine wichtige Deaktiverungsmöglichkeit darstellt, diese Überlegung veranlasste uns Trialkylphosphane mittlerer Größe, mit Substituenten die nur schwer eine Cyclometallierungen eingehen können zu testen. Die Verwendung der Phosphoniumsalze 4h (R = Cy, R‘ = neopentyl) und 4m (R = iPr, R‘ = CH2Cy) führt zu höheren Aktivitäten in der Suzuki-Miyaura Kreuzkupplung, als bestes Katalysatorsystem hat sich die Kombination aus Pd2(dba)3 oder Pd(OAc)2 und entsprechendem Phosphoniumsalz ergeben. Im zweiten Teil dieser Arbeit werden Synthesen zu neuen biphenylbasierten Diphosphanen (70, 71, 76, and 77) vorgestellt. Die Palladiumkomplexe wurden ebenfalls auf ihre Eignung als Katalysatoren in palladiumkatalysierten Suzuki-Miyaura Kreuzkupplungen getestet und zeigen für diese Klasse von Komplexen gute Aktivität. Das Tetraphosphan 82 wurde für die Synthese des zweikernigen Palladium(II)-komplex 83 eingesetzt. Durch die Koordination des D2h-symmetrischen Tetraphosphanes an die Palladiumatome wird die Symmetrie des Moleküls erniedrigt und folglich erhält man den formal D2-symmetrischen Komplex 83. / In the first part of this thesis, the synthesis and catalytic activity of neopentyl and neosilyl substituted phosphine palladium complexes is described. The complexes have been tested in the Suzuki-Miyaura cross-coupling reaction. Whereas the neosilyl substituted phosphines form 2:1 adducts (5b and 5d) with Palladium salts which showed moderate activity, the neopentyl complexes quickly undergo cyclometallation in presence of bases to form Palladacycles (6a, 6e, and 6g) which showed only moderate catalytic activity. Cyclometallation could be avoided by the preparation starting from Pd(cod)Cl2 in the absence of bases. The obtained 2:1 phosphine adducts showed superior activity. We concluded that cyclometallation process is an important deactivation pathway, this prompted us to test trialkyl phosphine ligands with medium size but substituents not reliable to cyclometallation. We have been pleased to find that 4h (R = Cy, R‘ = neopentyl) and 4m (R = iPr, R‘ = CH2Cy) showed good activity in the Suzuki-Miyaura cross-coupling reaction. The best results have been obtained by in situ preparation of active catalyst from Pd2(dba)3 or Pd(OAc)2 and the appropriate phosphonium salt. In the second part of this thesis, the first synthesis of a new family of biphenyl based bisphosphine ligands (70, 71, 76, and 77) has been reported. Their palladium complexes were successfully tested as catalyst in the Suzuki cross-coupling reaction. Within the class of bisphosphine based palladium complexes they show good activity in Suzuki-Miyaura cross-coupling reaction. Systematically, was expanded our synthesis strategy and we were able to introduce the first synthesis of a highly symmetric 2,2',6,6'-tetraphosphinobiphenyl. Tetraphosphine 82 was used as ligand in a dinuclear palladium(II) complex 83. Upon complexation the D2h symmetric 2,2’,6,6’-tetraphosphine lead to a chiral D2 symmetric complex 83.

Im ersten Teil der Arbeit wird die Synthese neopentyl- und neosilylsubstituierter Phosphane zur Verwendung als Liganden in katalytisch aktiven Palladiumkomplexen beschrieben. Die Aktivität wurde in der Suzuki-Miyaura Kreuzkupplungsreaktion getestet. Während die neosilylsubstituierten Phosphane 2:1 Addukte (5b und 5d) mit geeigneten Palladiumsalzen bilden, welche moderate Katalyseaktivität zeigen, untergehen die neopentylsubstituierten Komplexe schnelle Cyclometalierungsreaktionen in Gegenwart von Basen und bilden die katalytisch wenig aktiven Palladacyclen (6a, 6e, and 6g). Die deaktivierende Cylometallierung konnte durch Darstellung der Palladiumcomplexe ausgehend von Pd(cod)Cl2 in Abwesenheit von Basen vermieden werden. Die erhaltenen 2:1 Phosphaneaddukte zeigten deutlich verbesserte Aktivität. Daraus wurde geschlossen, dass die Cyclomettalierung als Nebenreaktion eine wichtige Deaktiverungsmöglichkeit darstellt, diese Überlegung veranlasste uns Trialkylphosphane mittlerer Größe, mit Substituenten die nur schwer eine Cyclometallierungen eingehen können zu testen. Die Verwendung der Phosphoniumsalze 4h (R = Cy, R‘ = neopentyl) und 4m (R = iPr, R‘ = CH2Cy) führt zu höheren Aktivitäten in der Suzuki-Miyaura Kreuzkupplung, als bestes Katalysatorsystem hat sich die Kombination aus Pd2(dba)3 oder Pd(OAc)2 und entsprechendem Phosphoniumsalz ergeben. Im zweiten Teil dieser Arbeit werden Synthesen zu neuen biphenylbasierten Diphosphanen (70, 71, 76, and 77) vorgestellt. Die Palladiumkomplexe wurden ebenfalls auf ihre Eignung als Katalysatoren in palladiumkatalysierten Suzuki-Miyaura Kreuzkupplungen getestet und zeigen für diese Klasse von Komplexen gute Aktivität. Das Tetraphosphan 82 wurde für die Synthese des zweikernigen Palladium(II)-komplex 83 eingesetzt. Durch die Koordination des D2h-symmetrischen Tetraphosphanes an die Palladiumatome wird die Symmetrie des Moleküls erniedrigt und folglich erhält man den formal D2-symmetrischen Komplex 83. / In the first part of this thesis, the synthesis and catalytic activity of neopentyl and neosilyl substituted phosphine palladium complexes is described. The complexes have been tested in the Suzuki-Miyaura cross-coupling reaction. Whereas the neosilyl substituted phosphines form 2:1 adducts (5b and 5d) with Palladium salts which showed moderate activity, the neopentyl complexes quickly undergo cyclometallation in presence of bases to form Palladacycles (6a, 6e, and 6g) which showed only moderate catalytic activity. Cyclometallation could be avoided by the preparation starting from Pd(cod)Cl2 in the absence of bases. The obtained 2:1 phosphine adducts showed superior activity. We concluded that cyclometallation process is an important deactivation pathway, this prompted us to test trialkyl phosphine ligands with medium size but substituents not reliable to cyclometallation. We have been pleased to find that 4h (R = Cy, R‘ = neopentyl) and 4m (R = iPr, R‘ = CH2Cy) showed good activity in the Suzuki-Miyaura cross-coupling reaction. The best results have been obtained by in situ preparation of active catalyst from Pd2(dba)3 or Pd(OAc)2 and the appropriate phosphonium salt. In the second part of this thesis, the first synthesis of a new family of biphenyl based bisphosphine ligands (70, 71, 76, and 77) has been reported. Their palladium complexes were successfully tested as catalyst in the Suzuki cross-coupling reaction. Within the class of bisphosphine based palladium complexes they show good activity in Suzuki-Miyaura cross-coupling reaction. Systematically, was expanded our synthesis strategy and we were able to introduce the first synthesis of a highly symmetric 2,2',6,6'-tetraphosphinobiphenyl. Tetraphosphine 82 was used as ligand in a dinuclear palladium(II) complex 83. Upon complexation the D2h symmetric 2,2’,6,6’-tetraphosphine lead to a chiral D2 symmetric complex 83.

Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008. / N,N-dialkyl-N-acyl(aroyl)thiourea ligands form stable chelated complexes in a cis configuration with the platinum group metals. Such chelated complexes are generally considered substitutionally “inert” in solution, however, it was found that cis-bis(N,Ndialkyl- N-acyl(aroyl)thioureato)M(II) complexes (M = Ni(II), Pd(II) or Pt(II)) readily undergo facile chelate metathesis reactions in solution at room temperature. Upon mixing two different parent complexes, a mixed-ligand product formed in solution, with an equilibrium, or steady state, between the two parent complexes and the mixed-ligand product being attained after a period of time: M(LA)2 + M(LB)2 M(LA)(LB). All three complexes remained in solution even with a ten-fold excess of one parent complex. The presence of the mixed-ligand products in solution was confirmed by liquid chromatography-mass spectrometry (LC-MS), nuclear magnetic resonance (NMR) spectra and a crystal structure of the mixed-ligand complex cis-Pd(L3-S,O)(L4-S,O). Though a number of attempts were made, it was not possible to either isolate or synthesise the mixed-ligand complexes exclusively. The equilibrium distribution and the rate of the metathesis reaction were influenced by a number of factors, including the central metal ion, the substituents on the complexed ligands and the reaction medium. In addition to these, a number of other factors, some unexpected, also played a role in the rate of the reaction. Initial concentration of the parent complexes, the age of the solutions upon mixing and the presence of impurities or additives all contributed to the overall rate of reaction. The results from these rate studies highlighted the necessity for extensively purified compounds. In addition to chelate metathesis reactions, the exchange between a cis-Pd(L-S,O)2 complex and an unbound HL ligand in solution was also investigated. Again, even with an excess of unbound ligand, all three possible complexes were present in solution. It has been shown previously that these complexes undergo a photoinduced cis-trans isomerisation under intense light, and it has been proposed that the reverse trans-cis process, which occurs in the dark, may be a metathesis reaction. In light of this, the relationship between these chelate metathesis reactions and the reverse trans-cis reaction was briefly investigated. Though the metathesis reactions were a general phenomenon in the Ni(II), Pd(II) and Pt(II) complexes of the aforementioned ligands, the experiments focused mainly on the cis-Pd(L-S,O)2 complexes due to the favourable timescales of their metathesis reactions. The primary technique to observe these reactions was reversed-phase high-performance liquid chromatography (rp-HPLC). The timescales involved in the cis-Pd(L-S,O)2 metathesis reactions as well as the stability of the Pd(II) complexes under the HPLC conditions made this technique ideal.

Title: Homologous ferrocene phosphines Author: Bc. Petr Vosáhlo Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: This thesis describes the synthesis and coordination behaviour of ferrocene diphosphines derived from 1,1'-bis(diphenylphosphino)ferrocene (dppf). Dppf is one of the most succesful ferrocene ligands, which can be used in various metal-catalyzed reactions. This study aimed to prepare analogous ligands with one dialkylphosphino substituent and one (diphenylphosphino)methyl group. These ligands were oxidized by KSeCN to afford the corresponding phosphinoselenides. The phosphinoselenides were used to assess sigma-donor abilities by measuring the coupling constant 1 JSeP via 31 P NMR spectroscopy. Lastly, the coordination behaviour of these ligands in palladium complexes was studied. The homologous ligands usually formed a mixtures containing a chelate complex and dimeric species with trans- coordinated ligands. Key words: ferrocene, phosphines, homologous ligands, palladium(II) complexes, structure elucidation.

Sustainable chemical processes are becoming increasingly important in all fields of synthetic chemistry. Catalysis can play an important role in developing environmentally benign chemical processes, and transition metals have an important role to play in the area of green chemistry. In particular, palladium(II) catalysis includes many key features for successful green chemistry methods, as demonstrated by a number of eco-friendly oxidation reactions catalyzed by palladium(II). The aim of the work presented in this thesis was to develop novel and greener palladium(II)-catalyzed coupling reactions. In striving to achieve this aim, the first open-vessel, room-temperature palladium(II)-catalyzed oxidative Heck reaction, using oxygen from the air as the reoxidant of palladium, was developed. In a further investigation of the palladium(II)-catalyzed oxidative Heck reaction, base-free conditions for the transformation were identified and suitable conditions for microwave-assisted oxidative Heck reactions were established. A convenient and low-cost palladium(II)-catalyzed method for the synthesis of styrene derivatives, by coupling arylboranes with vinyl acetate, was developed. The reaction mechanism was studied using ESI-MS, which enabled the detection of cationic palladium intermediates in ongoing productive reactions, and a plausible catalytic cycle was proposed. In an attempt to make the oxidative Heck and the styrene synthesis reactions more attractive from an industrial point of view, conditions for continuous flow synthesis were identified. The results were generally good and rapid synthesis of the desired products was obtained. The first palladium(II)-catalyzed C–P bond-forming Hirao-type reaction, employing arylboranes instead of the commonly used aryl halides, was developed. An ESI-MS study was performed, and a plausible catalytic pathway was suggested. Finally, a novel method for synthesizing aryl ketones from benzoic acids and nitriles, via palladium(II)-catalyzed decarboxylation of the benzoic acids, was established. Further, the reaction mechanism was studied by ESI-MS and a plausible catalytic route presented.

Die vorliegende Arbeit befasst sich mit der Synthese, dem Reaktionsverhalten, den Festkörperstukturen und den elektronischen Eigenschaften von neuartigen Übergansmetall-komplexen der Gruppen 4, 8 und 10 des Peridoensystems der Elemente. Die Arbeit befasst sich unter anderem mit der Darstellung von Alkyloxy- und Aryloxy-substituierten Titanocenverbindungen des Typs [Ti](Cl)(OR) {[Ti] = (C5H5SiMe3)2Ti; R = organischer Rest). Mittels cyclovoltammetrischer Experimente und anhand von Festkörpestrukturen wird der elektronische Einfluss der organischen Reste auf das Metallzentrum untersucht. Weiterhin befasst sich die Arbeit mit der Synthese von in para-Position substituierten NCN-Pincerverbindungen. Durch die Wahl des Substituenten in para-Postition sowie des Übergangsmetalls der Gruppe 10 des Periodensystems der Elemente ist es möglich, verschiedenartig gerichtete polymere Strukturen zu bilden. Ein weiterer Schwerpunkt der vorliegenden Arbeit liegt in der Synthese und Untersuchung der elektronischen Eigenschaften von NCN-Pincer-substituierten Ferrocenen. Der Einfluss der NCN-Pincer auf die Elektronendichte des Ferrocens wird bestimmt sowie die Eignung derartiger Systeme als elektrochemische Sensoren zur molekularen Erkennung von Schwefeldioxid wird untersucht.