Unsymmetrical pincer-type ruthenium complex containing β-protic pyrazole and N-heterocyclic carbene arms: comparison of Brønsted acidity of NH groups in second coordination sphere.

A reaction of a 2-(imidazol-1-yl)methyl-6-(pyrazol-3-yl)pyridine with [RuCl2 (PPh3 )3 ] resulted in tautomerization of the imidazole unit to afford the unsymmetrical pincer-type ruthenium complex 2 containing a protic pyrazole and N-heterocyclic carbene (NHC) arms. Deprotonation of 2 with one equivalent of a base led to the formation of the NHC-pyrazolato complex 3, indicating that the protic NHC arm is less acidic. When 2 was treated with two equivalents of a base under H2 or in 2-propanol, the hydrido complex 4 containing protic NHC and pyrazolato groups was obtained through metal-ligand cooperation.