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The CÀ F bond of acyl fluorides can be cleaved and added across tethered alkenes in the presence of a cationic rhodium(I) tetrafluoroborate catalyst. This 1,2carbofluorination reaction offers a powerful method for the synthesis of tertiary alkyl fluoride derivatives with an atom economy of 100 %. Mechanistic studies indicate that the concerted action of a rhodium cation and a tetrafluoroborate anion is key for the success of this catalytic cleavage and formation of CÀ F bonds in a controlled manner.

The cyclodimerization of diphenylacetylene derivatives catalyzed by a platinum-silylene complex is reported. The reaction proceeds via the cleavage of a carbon-hydrogen bond at the ortho-position of an alkynyl group and no additives are needed. Platinum complexes bearing other common ligands, such as phosphines and NHCs, failed to promote this reaction, highlighting the utility of the silylene ligand in this reaction.

The rhodium-catalyzed decarbonylation of acylsilanes is reported. This reaction proceeds through the cleavage of a carbon-silicon bond in acylsilanes. When two different acylsilanes are reacted in one batch, crossover products are formed. These results indicate that two mechanisms are operating in this catalytic reaction.