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A New Route to Azadithiolato Complexes



The reaction of [(MeC5H4)2Ti(SH)2] with cyclic imines with the formula (CH2NR)3 gives 2-aza-1,3-dithiolato chelate complexes [(MeC5H4)2Ti{(SCH2)2NR}] (1, R = Ph; 2, R = Me; 3, R = CH2Ph). These compounds demonstrate that azadithiolate ligands can exist on mononuclear metal centers. The complexes were characterized by 1H NMR spectroscopy, ESI-mass spectrometry, and X-ray crystallography. Variable-temperature 1H NMR studies reveal that the dithiolate ligands undergo ring inversion like other dithiatitanacyclohexanes. Treatment of [(MeC5H4)2Ti{(SCH2)2NPh}] (1) with [Fe(benzylideneacetone)(CO)3] afforded [Fe2{(SCH2)2NPh}(CO)6] in good yield.

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