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Synthesis of new organometallic fragments for organic molecules functionalization

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Synthesis of new organometallic fragments for organic molecules functionalization

Talavera Nevado, Maria
 
DATE : 2014-04-04
UNIVERSAL IDENTIFIER : http://hdl.handle.net/11093/144
UNESCO SUBJECT : 2303.21 Compuestos Organometálicos
DOCUMENT TYPE : doctoralThesis

ABSTRACT :

This memory consists of five chapters; each of them includes a short introduction, a discussion and partial conclusions. In Chapter 1 it is presented the synthesis and characterization of a new set of hydride complexes. Protonation reactions were realized to these hydrides and a study of their nature was also done. These hydrides do not show reactivity with organic molecules which suggests the search of another kind of precursor. Thus, in Chapter 2 an (acetonitrile)iridium complex was used as starting material (due to the lability of the solvate ligand allowing the creation of a new coordination vacant site) for the synthesis of the (methoxy)alkenylcarbeneiridium complex [IrCp*Cl{=C(OMe)CHCPh2}(PPh2Me)]PF6. Furthermore, in this chapter experimental and theoretical studies of the reactivity of this complex with different amines are described. Keeping on the study of the reactivity of the (methoxy)alkenylcarbeneiridium complex, Chapter 3 is focused on the synthesis of the iridanaphthalene complexes [IrCp*{=C(OMe)CH=CPh(o–C6H4)}(L)]PF6 (L = PPh2Me, PMe3) through an i ... [+]
This memory consists of five chapters; each of them includes a short introduction, a discussion and partial conclusions. In Chapter 1 it is presented the synthesis and characterization of a new set of hydride complexes. Protonation reactions were realized to these hydrides and a study of their nature was also done. These hydrides do not show reactivity with organic molecules which suggests the search of another kind of precursor. Thus, in Chapter 2 an (acetonitrile)iridium complex was used as starting material (due to the lability of the solvate ligand allowing the creation of a new coordination vacant site) for the synthesis of the (methoxy)alkenylcarbeneiridium complex [IrCp*Cl{=C(OMe)CHCPh2}(PPh2Me)]PF6. Furthermore, in this chapter experimental and theoretical studies of the reactivity of this complex with different amines are described. Keeping on the study of the reactivity of the (methoxy)alkenylcarbeneiridium complex, Chapter 3 is focused on the synthesis of the iridanaphthalene complexes [IrCp*{=C(OMe)CH=CPh(o–C6H4)}(L)]PF6 (L = PPh2Me, PMe3) through an intramolecular C–H activation of one of the phenyl rings of the alkenylcarbene ligand. Besides, it is shown the evolution of these complexes into 3-phenylindan-1-one via an indenyl intermediate. In the following chapters it is deeply studied the cyclometalation reaction of different (methoxy)alkenylcarbeneiridium complexes. Thus, in Chapter 4, it is described how (methoxy)alkenylcarbene complexes undergo an intramolecular C–H activation of one of the R substituents of the alkenyl fragment leading to iridacyclopentadienes. On the other hand, Chapter 5 is focused on the formation of a set of iridanaphthalene complexes with different substituents in the phenyl rings of the carbene ligand and their influence in the stability of them. In General Conclusions it is shown the most relevant results of this work. Finally, details of each technique used and the preparation and characterization of all new complexes are described in the Experimental Part. [-]

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