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By Elena Soriano, José Marco-Contelles

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31 Carbophilic Lewis Acids: Reactivity Principles . . . . . . . . . . . . . . . . . . . . . . 32 Enyne Cycloisomerization Reactions in the Absence of Nucleophiles . . . . . . . . . . 1 Formation of Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Conia Ene Type Reactions . . . . . . . . . . . . . . . . . . . .

3 Nitrogen Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 1 Introduction Metal-catalyzed cycloisomerization reactions of 1,n-enynes have appeared as conceptually and chemically highly attractive processes as they contribute to the thrill towards atom economy and offer the opportunity to develop new reactions [1–8].

This dative bond is counterbalanced by overlap of a metal dxz orbital with the empty px orbital of the ligand to form the p bond. In other words, Au as well as Pt can engage in electron back-donation from the metal atom to a carbene ligand. This picture contrasts the low ability of the same metal templates to back-donate into the p* orbital of an alkyne or alkene ligand. ” To get deeper insights into the nature of the chemical bond in gold-carbenes, Frenking and co-workers [146] analyzed mixed carbene–halogen and bis(carbene) complexes at the BP86 level of theory using an energy decomposition analysis (EDA) with the simple imidazol-1-ylidene as model carbene ligand.

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