A series sterically-encumbered coumarin-(1) and chrysin-functionalized triazolium salts (2,3) have been synthesized stepwise via copper catalyzed alkyne-azide cycloaddition and N-alkylation procedures. Their one-pot deprotonation with KHMDS in presence of AuCl(SMe 2 ) allowed for the preparation of the corresponding triazolylidene gold(I) complexes (4-6) in high yields (75-92 %). All new compounds were fully character- [a] 4622 Scheme 2. Synthesis of coumarin-functionalized salt 1.Scheme 3. Synthesis of chrysin-functionalized mono-triazolium 2. Figure 2. Molecular structure of coumarin-functionalized MIC-gold complex 4. Ellipsoids are shown at 50 % probability.Scheme 6. Synthesis of the chrysin-derived dinuclear complex 6.

The reaction of 4-substituted imidazol-2-ylidenes with various electrophiles produces a series of 2,4-functionalized imidazolium salts. Subsequent metalation of these precursors using AuCl(SMe) provides the first examples of highly functionalized abnormal carbenegold(I) complexes. The present protocol introduces a new strategy for the synthesis of metallic abnormal carbenes featuring diverse functional groups.

We report the straightforward synthesis and full characterization of a novel series rhodium(I) complexes (3 a-c) supported by hydroxyl-functionalized 1,2,3-triazolylidenes. All new compounds were fully characterized by means of 1 H and 13 C NMR spectroscopy, melting points, and elemental analyses. The new triazolylidene rhodium complexes 3 a-c were tested as catalysts in the hydrosilylation of terminal alkynes and the 1,4-addition of boronic acid to 2-cyclohexenone. Both catalytic processes provide good to excellent yields under low catalyst loadings and in the case of the hydrosilylation, a good selectivity toward the E-isomer is observed.