Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of [Mo(CO)₂(η²‐S₂COEt)(η²‐SCNMe₂)(PPh₃)] and [Mo(CO)₂(η²‐S₂CNC₄H₈)(η²‐SCNMe₂)(PPh₃)]

The reaction of the thiocarbamoyl‐molybdenum complex [Mo(CO) 2 (η 2 ‐SCNMe 2 )(PPh 3 ) 2 Cl] 1 , with EtOCS2K and C4H8NCS2NH4 in dichloromethane at room temperature yielded the seven coordinated ethyldithiocarbonate thiocarbamoyl‐molybdenum complex [Mo(CO) 2 (η 2 ‐S 2 COEt)(η 2 ‐SCNMe 2 )(PPh 3 )] 2 , and the dithiocarbamate thiocarbamoyl‐molybdenum complex [Mo(CO) 2 (η 2 ‐S 2 CNC 4 H 8 )(η 2 ‐SCNMe 2 )(PPh 3 )] 3 . The geometry around the metal atom of compounds 2 and 3 are capped octahedrons as revealed by X‐ray diffraction analyses. The thiocarbamoyl and ethyldithiocarbonate or pyrrolidinyldithiocarbamate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, respectively. Structure parameters, NMR, IR and Mass spectra are in agreement with the crystal chemistry of the two compounds.