Isolation of Mo/S/Ag Cluster Complexes from Self‐Assembly Reaction of Dinuclear Molybdenum [Et₄N]₂[(pdt)₂Mo₂S₂(<i>μ</i>‐S)₂] (pdt = ⁻SCH₂CH(CH₃)S<sup>−

Abstract A dinuclear molybdenum precursor [Et 4 N] 2 [(pdt) 2 Mo 2 S 2 ( μ ‐S) 2 ] (pdt = 1,2‐propanedithiol dianion) ( 1 ) was generated by combining mononuclear molybdenum‐sulfur starting complex (NH 4 ) 2 MoS 4 with one equimolar of pdtH 2 and Et 4 NBr in DMF (DMF = N , N′ ‐dimethylformamide). Treatment of complex 1 with two equimolar of AgCl in the presence of a little excess DPEPhos (DPEPhos = bis(2‐diphenylphosphinophenyl)ether) and dppm (dppm = bis(diphenylphosphino)methane) in a CH 3 OH/DMF mixed solution, resulting isolation of two formed cluster complexes [(pdt) 2 Mo 2 S 2 ( μ ‐S) 2 Ag 2 (DPEPhos) 2 ]·0.5CH 3 OH·2DMF ( 2 ) and [(pdt) 2 Mo 2 S 2 ( μ ‐S) 2 Ag 2 (dppm) 2 ]·0.5CH 3 OH·3DMF ( 3 ), respectively. Complexes 1–3 have been characterized by infrared, 1 H and 31 P NMR, UV–vis, and fluorescence spectroscopies. Moreover, molecular structures of complexes 1–3 have been established by single‐crystal X‐ray crystallography.