4,4'-Disubstituted-2,2'-bipyridine ligands coordinated to Mo and Re cationic fragments become dearomatized by an intramolecular nucleophilic attack from a deprotonated N-alkylimidazole ligand in cis disposition. The subsequent protonation of these neutral complexes takes place on a pyridine carbon atom rather than at nitrogen, weakening an aromatic C-C bond and affording a dihydropyridyl moiety. Computational calculations allowed for the rationalization of the formation of the experimentally obtained products over other plausible alternatives.

Compounds containing N‐alkylimidazoles (N‐RIm) and 4,4′‐disubstituted 2,2′‐bipyridines (4,4′‐R′2bipy) coordinated to cationic {Mo(η3‐C4H7)(CO)2} and {Re(CO)3} fragments undergo deprotonation of the C2‐H group of the N‐RIm ligands in their reactions with KN(SiMe3)2. The resulting internal nucleophile adds either to one pyridyl ring, which becomes dearomatized and can undergo ring opening in the subsequent reaction with excess MeOTf, or to the metal center, yielding imidazol‐2‐yl complexes, which in turn add HOTf or MeOTf, affording N‐heterocyclic carbene complexes. Which pathway is followed is dictated by the metal and the nature of the imidazole (R) and bipyridine (R′) substituents. For ReI compounds, addition to pyridine is found with R′=tBu and OMe, whereas for R=Me and R′=NMe2, imidazolyl formation is preferred. Coordination of 4,7‐Cl2‐1,10‐phenanthroline to MoII favors C−C coupling, in contrast to the analogous parent bipy or phenanthroline complexes, for which formation of the imidazol‐2‐yl complexes had been found. DFT calculations showed the theoretically expected products in each case, and following their predictions new types of products were obtained experimentally.

Unsupported 1-methyl-1,2,3-triazole has been coordinated to {Mo(η -methallyl)(CO) (N-N)} (N-N=2,2'-bipyridine, bipy; or 1,10-phenanthroline, phen) fragments, yielding cationic complexes that can be regarded as metalated triazolium salts. Their reactivity towards a strong base led to the deprotonation of the C5-H group of the triazole moiety, followed by an intermolecular nucleophilic attack to the ortho CH group of a bipy or phen ligand affording cyclic, bimetallic dearomatized C-C coupling products. The reaction of the neutral bipy derivative with an acid led to the formation of dihydropyridyl units by protonation of a CH group of the dearomatized rings, the dimeric nature of complexes being mantained upon protonation.

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