The hitherto unknown complexes, [M 2 (CO) 6 -(l-CO)(l-L)], [M = Cr; 1, Mo; 2, W; 3] and [M 2 (CO) 6 -(l-CO)(l-L 0 )], [M = Cr; 4, Mo; 5, W; 6] have been synthesized by the photochemical reactions of photogenerated intermediate, M(CO) 5 THF (M = Cr, Mo, W) with thio Schiff base ligands, N,N 0 -bis(2-aminothiophenol)-1,4-bis(2-carboxaldehydephenoxy)butane (H 2 L) and N,N 0 -bis(2-aminothiophenol)-1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane (H 2 L 0 ). The complexes have been characterized by elemental analysis, LC-mass spectrometry, magnetic studies, FT-IR and 1 H NMR spectroscopy. The spectroscopic studies show that H 2 L and H 2 L 0 ligands are converted to benzothiazole derivatives, L and L 0 after UV irradiation and coordinated to the central metal as bridging ligands via the central azomethine nitrogen and sulphur atoms in 1-6.