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The study of normal N-heterocyclic carbenes (NHCs), which probably represent one of the most important families of ligands in organometallic chemistry and homogeneous catalysis, has indubitably led to the usage of other related ligands beyond di-amino carbenes. So far, such species are only marginally used as ligands due to their relative novelty and stability. The following chapters describe the exciting journey into the development of new synthetic accesses of various abnormal, remote N-heterocyclic, mesoionic and carbocyclic carbene transition metal complexes. The uses of a number of these ruthenium- and copper-based complexes as catalysts in several applications are also disclosed. Halfway between the study of the electronic effect of mixed NHC/phosphite ruthenium in olefin metathesis reactions (Chapter 1) and NHC copper-catalysed transformations (Chapters 5 and 6), resides the core of this dissertation that links the book end chapters. Indeed, the NHC-Cuᴵ transfer or “transmetalation” reaction is disclosed as a powerful and reliable tool to access new transition metal catalysts in a relatively general manner. The syntheses of a series of various non-conventional NHC-Cu complexes as precursors for the transmetalation reaction are also described in Chapter 2. The dissertation finally closes with some preliminary results on what represents the first experimental and theoretical evidence for the mechanism of the NHC transfer by transmetalation. The exploration of the reaction by exchange from copper to platinum has begun to reveal what was so far unknown through the isolation of reactive intermediate species formed during the process.

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