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Gold is currently one of the most used metals in organometallic catalysis. The ability of gold to activate unsaturated groups in different modes, together with its tolerance to a wide range of functional groups and reaction conditions, turns gold-based complexes into efficient and highly sought after catalysts. Natural products and relevant compounds with biological and pharmaceutical activity are often characterized by complex molecular structures. (Cyclo)isomerization reactions are often a useful strategy for the generation of this molecular complexity from synthetically accessible reactants. In this review, we collect the most recent contributions in which gold(I)- and/or gold(III)-catalysts mediate intramolecular (cyclo)isomerization transformations of unsaturated species, which commonly feature allene or alkyne motifs, and organize them depending on the substrate and the reaction type.

Oxygen atom transfer reactions are receiving increasing attention because they bring about paramount transformations in the current biomass processing industry. Significant efforts have therefore been made lately in the development of efficient and scalable methods to deoxygenate organic compounds. One recent alternative involves the modification of the Cadogan reaction in which a Mo(VI) core catalyzes the reduction of o -nitrostyrene derivatives to indoles in the presence of PPh 3 . We have used density functional theory calculations to perform a comprehensive mechanistic study on this transformation, in which we find two clearly defined stages: an associative path from the nitro to the nitroso compound, characterized by the reduction of the catalyst in the first step, and a peculiar mechanism involving oxazaphosphiridine and nitrene intermediates leading to an indole product, where the metal catalyst does not participate., Competing Interests: The authors declare no competing financial interest.

A theoretical study of the cooperativity in linear chains of (H3SiCN)n and (H3SiNC)n complexes connected by tetrel bonds has been carried out by means of MP2 and CCSD(T) computational methods. In all cases, a favorable cooperativity is observed, especially in some of the largest linear chains of (H3SiNC)n, where the effect is so large that the SiH3 group is almost equidistant to the two surrounding CN groups and it becomes planar. In addition, the combination of tetrel bonds with other weak interactions (halogen, chalcogen, pnicogen, triel, beryllium, lithium, and hydrogen bond) has been explored using ternary complexes, (H3SiCN)2:XY and (H3SiNC)2:XY. In all cases, positive cooperativity is obtained, especially in the (H3SiNC)2:ClF and (H3SiNC)2:SHF ternary complexes, where, respectively, halogen and chalcogen shared complexes are formed.

A theoretical study of the beryllium bonds in BeR2:C6X6 (R = H, F, Cl and X = H and F) has been carried out by means of MP2/aug'-cc-pVDZ computational methods. In addition, the ternary complexes BeR2:C6X6:Y- (Y = Cl and Br) have been analyzed. Geometric, energetic and electronic aspects of the complexes have been taken into account. All the parameters analyzed provide a clear indication of favorable cooperativity in both interactions observed, beryllium bond and aromatic ring:anion interaction.