A New Route to Azadithiolato Complexes.

The reaction of [(MeC(5)H(4))(2)Ti(SH)(2)] with cyclic imines with the formula (CH(2)NR)(3) gives 2-aza-1,3-dithiolato chelate complexes [(MeC(5)H(4))(2)Ti{(SCH(2))(2)NR}] (1, R = Ph; 2, R = Me; 3, R = CH(2)Ph). These compounds demonstrate that azadithiolate ligands can exist on mononuclear metal centers. The complexes were characterized by (1)H NMR spectroscopy, ESI-mass spectrometry, and X-ray crystallography. Variable-temperature (1)H NMR studies reveal that the dithiolate ligands undergo ring inversion like other dithiatitanacyclohexanes. Treatment of [(MeC(5)H(4))(2)Ti{(SCH(2))(2)NPh}] (1) with [Fe(benzylideneacetone)(CO)(3)] afforded [Fe(2){(SCH(2))(2)NPh}(CO)(6)] in good yield.