Síntesis, caracteización y reactividad de complejos de Pd(II) con Ligandos Arilo sustituidos en Orto : aplicaciones en síntesis orgánica.

Se describe la síntesis de una serie de complejos de Pd(II) con ligandos arilo que contienen en orto los grupos vinilo (CH=CH2), formilo (CHO), acetilo (C(O)Me) y nitrilo (CN), sin sustituyentes adicionales, y se estudia su reactividad frente a moléculas insaturadas: alquinos, isocianuros y monóxido de carbono. De esta forma se obtienen compuestos orgánicos de interés, difíciles de preparar por otros métodos. La tesis contiene un capitulo dedicado a la investigación mediante Resonancia Magnética Nuclear del enlace C-Pd en estos complejos. El último capítulo describe la síntesis del primer ligando pincer derivado del ferroceno, para su uso en catalisis homogénea.The synthesis of a series of Pd(II) aryl complexes with vinyl (CH=CH2), formyl (CHO), acetyl (C(O)Me) and nitrile (CN) groups in ortho, is described. The reactivity of these complexes towards unsaturated molecules: alkynes, isocyanides and carbon monoxide, is investigated. The formation of interesting and otherwise difficult to obtain organic compounds is described. A chapter is dedicated to the investigation of the C-Pd bond in some of these complexes using Nuclear Magnetic Resonance. The last chapter describes the synthesis of the first ferrocene-derived pincer ligand, of interest in homogeneous catalysis

C-H Activation in Primary 3-Phenylpropylamines: Synthesis of Seven-Membered Palladacycles through Orthometalation. Stoichiometric Preparation of Benzazepinones and Catalytic Synthesis of Ureas

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00542The dimeric cyclometalated complexes [Pd2{C,N-C6H4CH2CH2C(R)(Me)NH2-2}2(µ-Cl)2] (R = Me (1a), H (1b)) are prepared by reacting 1,1-dimethyl-3-phenylpropylammonium or 1-methyl-3-phenylpropylammonium triflate with Pd(OAc)2 in a 1:1 molar ratio, and subsequent treatment with excess NaCl. The mononuclear derivatives [Pd{C,N-C6H4CH2CH2C(R)(Me)NH2-2}Cl(L)] (L = PPh3, R = Me (3a), H (3b); L = 4-picoline (4-pic), R = Me (4a), H (4b)) were prepared from 1a,b, by splitting the chloro-bridges with the neutral ligands L. A conformational analysis of the mononuclear palladacycles in solution has been carried out. Insertion of CO takes place into the Pd–C bond of complexes 1a,b affording Pd(0) and the tetrahydro-benzazepinone 5a or 5b, which possesses potential pharmacological interest. Additionally, the triflate salt A or B undergoes catalytic carbonylation with CO to afford the corresponding N,N’-dialkylurea, using Pd(OAc)2/Cu(OAc)2, in boiling acetonitrile. The crystal structures of 3a·1/2H2O, 3b, 4b·CHCl3, and 5a were determined by X-ray diffraction studies