Dissociative pathway of the [Pd(2,2′-bipyridyl)(2-picoline)2]2+ cation

Cuboidal Mo3S4 and Mo3NiS4 Complexes Bearing Dithiophosphates and Chiral Carboxylate Ligands: Synthesis, Crystal Structure and Fluxionality

“…For example, for palladium complexes featuring 2,2Ј-bipyridyl and substituted pyridine ligands of general formula [Pd(bipy)(py) 2 ] 2+ or [Pt(bipy)(py) 2 ] 2+ , the mechanistic picture (dissociative exchange of hindered rotation-mediated pyridine exchange) of the pyridine exchange is dramatically affected by the identity of the substituent in the pyridine ligand and is associated with syn/anti inversion. [45][46][47] Note the distinctive lability of the Mo(3)-py and Ni(1)-py groups, the latter being exchanged (on the NMR timescale) only at high T (typically T Ͼ 90°C). In additional 1 H NMR experiments with an excess of C 5 D 5 N, immediate py replacement at the Mo(3) site takes place, whereas replacement at the Ni site is slower.…”