Complexos Diazenetos de Renio

In this work it has been investigated the synthesis of some diazenide, nitride and dinitrogen complexes of rhenium, in several oxidation (I to V). They were characterised by elemental analysis, infrared, nuclear magnetic resonance ("1He"3"1P) and, when possible, by X-ray diffraction analyses, electronic paramagnetic resonance, FAB-MS and cyclic voltammetry. Chapter two describes the synthesis of the diazenide complexes [ReCl(NNPh)_2(PPh_3)_2], [ReBr_2(NNPh)_2(PPh_3)_2(PPh_3)_2]Br, [ReBr_3(NNPh)(PPh_3)_2] and [ReBr_2(NNPh)_"(PPh_3)_2]. Their reactivity with nucleophiles, electrophiles, sulphurated species, carbon monoxide, phosphirene and some small species of biological relevance (isocyanides, nitriles, cyanamide and derived compounds, pseudo-halides and alkynes) was studied in chapter 3. Different reactions were observed: conversion of diazenide into diazene, hidrazide or nitride species and substitution of halides, diazene or phosphirene by different substrates, often with metal reduction. Also in this chapter the reactivity of the nitride-compound [ReNCl_2(PPh_3)_2] with isocyanide is discussed.Chapter four describes the reactivity of the benzoyl-diazenide [ReCl_2(NNCOPh)(PMePh_2)_3] and the derived dinitrogen [ReCl(N_2)(PMePh_2)_4] complexes with cyanamide and derived compounds and with phosphireneAvailable from Fundacao para a Ciencia e a Tecnologia, Servico de Informacao e Documentacao, Av. D. Carlos I, 126, 1200 Lisboa / FCT - Fundação para o Ciência e a TecnologiaSIGLEPTPortuga