Elucidation of the Pyridine Ring-Opening Mechanism of 2,2'-Bipyridine or 1,10-Phenanthroline Ligands at Re(I) Carbonyl Complexes.

The cleavage of the C-N bonds of aromatic heterocycles, such as pyridines or quinolines, is a crucial step in the hydrodenitrogenation (HDN) industrial processes of fuels in order to minimize the emission of nitrogen oxides into the atmosphere. Due to the harsh conditions under which these reactions take place (high temperature and H2 pressure), the mechanism by which they occur is only partially understood, and any study at the molecular level that reveals new mechanistic possibilities in this area is of great interest. Herein, we unravel the pyridine ring-opening mechanism of 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) ligands coordinated to the cis-{Re(CO)2(N-RIm)(PMe3)} (N-RIm= N-alkylimidazole) fragment under mild conditions. Computational calculations show that deprotonation of the pyridine ring, once dearomatized, is crucial to induce ring contraction, triggering extrusion of the nitrogen atom from the ring and cleavage of the C-N bond. It is noteworthy that different products (regioisomers) are obtained depending on whether the ligand used is bipy or phen due to the additional rigidity and stability conferred by the central ring of the phen ligand, an issue also addressed and clarified computationally. Strong support for the proposed mechanism is provided by the characterization and isolation, including three single-crystal X-ray diffraction structures, of several of the proposed reaction intermediates.

Strongly Electron-Donating Triazolylidene Ligands: Cationic Metal Carbonyl Complexes of 1-Methyl-1,2,3-triazole as Triazolium Surrogates.

A new strategy for tuning the electronic properties of 1,2,3-triazol-5-ylidene metal complexes is reported using {Mo(η3-C4H7)(bipy)(CO)2} or {Re(bipy)(CO)3} fragments as substituents at the triazole N3 atom. The reaction of cationic molybdenum(II) and rhenium(I) 1-methyl-1,2,3-triazole compounds with the strong base KN(SiMe3)2 in the presence of electrophilic metal fragments, such as AgOTf (OTf = trifluoromethanesufonate) or [CuCl(IPr)] [IPr = 2,6-(diisopropyl)phenylimidazol-2-ylidene] affords a new type of 1,2,3-triazol-5-ylidene complexes. For silver(I) cationic bis(triazolylidene), [Ag(tzNHCM)2]OTf (M = [Mo], 2; [Re], 4), complexes are obtained, whereas in the case of Cu(I) mixed normal/mesoionic NHC, [Cu(IPr)(tzNHCM)]OTf (M = [Mo], 7; [Re], 8) complexes are formed. This special type of mesoionic N-heterocyclic carbenes bear a metal fragment at the N3 atom of the 1,2,3-triazole moiety, showing notable enhancement of the carbene electron donor ability compared to conventional alkyl-substituted analogues. Transmetalation from cationic silver bis(triazolylidene) complexes 2 and 4, prepared using this methodology, has proven to be very efficient toward [M'Cl(cod)]2 (M' = Rh, Ir; cod = 1,5-cyclooctadiene), affording the corresponding cationic bis(triazolylidene) [M'(cod)(tzNHCM)2]OTf (9-12) complexes. A subsequent reaction with CO(g) easily produces substitution of the diene ligand, affording the corresponding cis-dicarbonyl [M'(CO)2(tzNHCM)2]OTf (13-16) compounds.