Construction of Mo/S/Ag Cluster Complexes from Dinuclear Molybdenum Precursors [R ₄ N] ₂ [(edt) ₂ Mo ₂ S ₂ ( <i>μ</i> ‐S) ₂ ] (R = Et, ⁿ Pr; edt = ⁻ SCH <sub>2</s

Abstract We have demonstrated that complexes [(edt) 2 Mo 2 O 2 (μ‐S) 2 Ag 2 (dppm) 2 ]·4CH 3 OH·DMF ( 2 , edt = 1,2‐ethanedithiolate dianion, dppm = bis(diphenylphosphino)methane, DMF = N,N‐dimethylformamide) and [(μ‐Cl) 2 Ag 4 (μ 3 ‐Cl) 2 (dppm) 2 ]·4DMF ( 3 ), were generated by combining a dinuclear molybdenum precursor [Et 4 N] 2 [(edt) 2 Mo 2 S 2 (μ‐S) 2 ] ( 1a ) with two equimolar AgCl and dppm in a CH 3 OH‐DMF mixed solution. Treatment of complex 1a with one equimolar AgCl and DPEPhos in CH 3 OH and DMF mixed solutions, producing complex [Et 4 N][(edt) 2 Mo 2 S 2 (μ‐S) 2 Ag(DPEPhos)]·CH 3 OH ( 4 , DPEPhos = bis(2‐diphenylphosphinophenyl)ether). Treatment of complex [ n Pr 4 N] 2 [(edt) 2 Mo 2 S 2 (μ‐S) 2 ] ( 1b ) with AgBr in acetonitrile followed by addition of (NH 4 ) 2 S produced a dodecanuclear Mo–Ag–S cage cluster [ n Pr 4 N] 2 [{Mo 2 Ag 2 S 2 O 2 (edt) 2 } 3 (μ 6 ‐S)]·1.5CH 3 CN ( 5 ). Complexes 2 − 5 have been characterized by infrared(IR), 1 H NMR, UV‐vis, and fluorescence spectroscopies. Moreover, molecular structures of complexes 2 − 5 have been established by single‐crystal X‐ray crystallography.