Pyridine ring-opening of a metal-coordinated 1,10-phenanthroline has been demonstrated for the first time. The reaction of stable, well-defined cis,trans-[Re(CO)2(N-N)(N-RIm)(PMe3)]OTf [N-N= 2,2’-bipyridine (bipy), N-RIm= N-alkylimidazole] compounds with KN(SiMe3)2, followed by the...

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A new strategy for tuning the electronic properties of 1,2,3-triazol-5-ylidene metal complexes is reported using {Mo(η 3 -C 4 H 7 )(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(SiMe 3 ) 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(tzNHC M ) 2 ]OTf (M = [Mo], 2; [Re], 4), complexes are obtained, whereas in the case of Cu(I) mixed normal/mesoionic NHC, [Cu(IPr)(tzNHC M )]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 = 1,5cyclooctadiene), affording the corresponding cationic bis(triazolylidene) [M′(cod)(tzNHC M ) 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 (tzNHC M ) 2 ]OTf (13−16) compounds.