Reaction of ruthenium complexes containing heterocyclic thiazine–thione ligand

Treatment of the ruthenium complex [Ru] (3, [Ru]=Cp(dppe)Ru) containing a heterocyclic [1,3]-thiazine-4-thione six-membered-ring ligand with various organic halides results in alkylation at the thione sulfur terminus of the ligand to yield [Ru]][X] (4a, R=CN, X=I; 4b, R=Ph, X=Br; 4c, R=CH=CH2, X=I, 4d, R=p-C6H4CF3, X=Br). Similarly the reaction of 3 with HgCl2 at room temperature affords [Ru]][Cl] (5). Transformation of 5 to the cationic vinylidene complex {[Ru]CC(Ph)C(O)NHPh}2[Hg2Cl6] (6) readily occurred in the air. The structures of 4c and 6 are determined by single crystal X-ray diffraction analysis.