000149996 001__ 149996
000149996 005__ 20190117220101.0
000149996 0247_ $$2doi$$a10.5075/epfl-thesis-4806
000149996 02470 $$2urn$$aurn:nbn:ch:bel-epfl-thesis4806-0
000149996 02471 $$2nebis$$a6108035
000149996 037__ $$aTHESIS
000149996 041__ $$aeng
000149996 088__ $$a4806
000149996 245__ $$aNovel Ruthenium Complexes with Sterically Demanding Cyclopentadienyl Ligands$$bSyntheses, Reactivity and Catalytic Applications
000149996 269__ $$a2010
000149996 260__ $$aLausanne$$bEPFL$$c2010
000149996 300__ $$a233
000149996 336__ $$aTheses
000149996 520__ $$aInvestigations of ruthenium halfsandwich complexes have mostly focused on Cp and Cp* based derivatives due to the availability of easily accessible starting materials. However, it is interesting to have complexes with substituted cyclopentadienyl ligands in order to study the influence of the π-ligand on the chemical behavior of the complexes, as well as to fine-tune their properties. During the course of this thesis, ruthenium complexes with novel, highly substituted cyclopentadienyl ligands ('Cp^') were prepared in one-pot syntheses from commercially available starting materials and under mild reaction conditions. The complexes are versatile starting materials leading to a variety of Cp^Ru complexes through facile ligand exchange reactions. The chemistry of Cp^Ru-complexes has been investigated and the general reactivity pattern was found to be similar to that of CpRu and Cp*Ru complexes. However, in several instances it was observed that the steric and electronic properties of the Cp^ ligand have a strong impact on the properties and chemical behavior of the complexes. As a consequence of the sterically demanding Cp^ ligand, coordinatively unsaturated complexes, that are otherwise inaccessible, have been stabilized. In addition, the presence of the Cp^ ligand resulted in unusual CO insertion reactions and in an unprecedented rearrangement of cyclooctadiene. Some Cp^Ru-complexes turned out to be very efficient catalysts for organic transformations such as the [2+2+2] alkyne cyclotrimerization and atom transfer radical cyclizations. Activation of molecular oxygen was also accomplished with Cp^Ru complexes. In vitro studies with Cp^Ru complexes have shown that they exhibit high cytotoxicity towards human cancer cell lines.
000149996 6531_ $$aRuthenium
000149996 6531_ $$aCyclopentadienyl
000149996 6531_ $$aHalf-sandwich
000149996 6531_ $$aHomogeneous catalysis
000149996 6531_ $$aRuthénium
000149996 6531_ $$aCyclopentadiényle
000149996 6531_ $$aDemi-sandwich
000149996 6531_ $$aCatalyse homogène
000149996 700__ $$0242597$$aDutta, Barnali$$g172099
000149996 720_2 $$0240333$$aSeverin, Kay$$edir.$$g145138
000149996 8564_ $$s3778874$$uhttps://infoscience.epfl.ch/record/149996/files/EPFL_TH4806.pdf$$yTexte intégral / Full text$$zTexte intégral / Full text
000149996 909C0 $$0252071$$pLCS$$xU10109
000149996 909CO $$ooai:infoscience.tind.io:149996$$pthesis-bn2018$$pDOI$$pSB$$pthesis$$qDOI2$$qGLOBAL_SET
000149996 918__ $$aSB$$cISIC$$dEDCH
000149996 919__ $$aLCS
000149996 920__ $$b2010
000149996 970__ $$a4806/THESES
000149996 973__ $$aEPFL$$sPUBLISHED
000149996 980__ $$aTHESIS