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Synthesis and characterization of non-oxo Mo(IV) complexes with the tetradentate thioether-thiol ligand 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(dttd-H 2 ) are reported. MoCl 4 (THF) 2  reacts with dttd-H 2  in THF at room temperature to give the paramagnetic (2.61 BM, 295 K) [Mo(dttd)Cl 2 ]. The chlorine ligands in [Mo(dttd)Cl 2 ] can be substituted by sulfur ligands yielding diamagnetic complexes as [Mo(dttd)(CeH 4 S 2 )], [Mo(dttd)(SC 2 H 4 S)] and [Mo(dttd)(SC 2 H 5 ) 2 ]; with Na 2 S, NaHS or H 2 S, the di-μ-sulfido bridged complex [(dttd)Mo(S) 2 Mo(dttd)] is obtained. The reduction of [Mo(dttd)Cl 2 ] by various reducing agents in the presence of CO or NO yields labile carbonyl and nitrosyl species in solution. In contrast to [Mo(dttd)Cl 2 ], the complexes with MoSe cbromophores showed no reactivity to CO or NO under reducing conditions.

zeitschrift für naturforschung b

Transition Metal Complexes with Sulfur Ligands, IV. Synthesis and Reactions of Mo (IV) Complexes with the Tetradentate Thioether-thiol Ligand 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane