The synthesis and characterization of novel six-and sevenmembered expanded ring N-heterocyclic carbene (NHC) complexes of the general formula [Au(NHC)Cl] are described. The key structural parameters of complexes 1, 2, and 4 have been evaluated by solid-state analysis and by means of the percent buried volume (%V bur ) analysis. Complex 4 is found to demonstrate the largest %V bur value of any gold(I) NHC complex reported to date, with a value of 52.6. All complexes 1−4 have been evaluated in a preliminary catalytic survey of the hydration of internal alkynes.

Starting from simple alkynes, sequential borylative cyclisation/electrophilic C–H borylation represents a simple modular route to novel B-doped PAHs.

In the presence of B(C6F5)3 five-membered heteroarenes undergo dehydrosilylation and hydrosilylation with silanes. The former, favoured on addition of a weak base, produces H2 as a by-product making the process catalytic in B(C6F5)3 but also enabling competitive heteroarene hydrogenation.

A series of well‐defined copper(I) complexes bearing ring‐expanded N‐heterocyclic carbene (NHC) ligands has been applied to the azide–alkyne cycloaddition reaction. The obtained results notably showed that the six‐membered NHC ligands outperform well‐established five‐membered ones. [CuI(Mes‐6)] displayed a remarkable catalytic activity while respecting the strict criteria for click reactions.

The direct C(sp(2) )-C(sp(3) ) cross-coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides proceeded in the absence of coordinating ethereal solvents at ambient temperature without the addition of a catalyst. The C(sp(2) )-C(sp(3) ) cross-coupling showed excellent functional-group tolerance, and products were isolated in high yields, generally without the requirement for purification by chromatography. This process represents an expedient, operationally simple method for the construction of new C(sp(2) )-C(sp(3) ) bonds.