Reactivity of a Methoxido-Ruthenium Complex Bearing a Pincer-Type Bis(carbene) Ligand toward Thiocyanate, Carbon Disulfide, and Isothiocyanate

Thiocyanate linkage isomers and two insertion complexes were prepared from a methoxido-ruthenium complex bearing a 2,6-bis(3-tert-butylimidazol-2-ylidene) pyridine (CNC) and a bipyridine ligand. In the mixture of the linkage isomers obtained from the substitution reaction, a linear N-bound and a bent S-bound isomer were crystallographically determined, and the equilibrium between them at elevated temperature was revealed. On the other hand, in reactions with carbon disulfide (CS2) and phenyl isothiocyanate (PhNCS), the S=C bond was inserted into the Ru-OMe bond, and the resulting ligands are bound to the ruthenium center by the sulfur atom.