Construction of Mo/S/Ag Cluster Complexes from Dinuclear Molybdenum Precursors [R4N]2[(edt)2Mo2S2(μ‐S)2] (R = Et, nPr; edt = −SCH2CH2S−)

• Published in: ChemistrySelect (Weinheim) 2024-10, Vol.9 (37), p.n/a
• Main Authors: Chen, Meng‐Ting, Liang, Qing‐Wen, Pan, Song, Shi, Hua‐Tian, Jia, Ai‐Quan, Zhang, Qian‐Feng
• Format: Article
• Language: English
• Subjects: Coordination complex; Hetero‐bimetallic cluster; Mo−Ag−S cage cluster; Spectroscopic property
• ISSN: 2365-6549; 2365-6549
• DOI: 10.1002/slct.202403160

We have demonstrated that complexes [(edt)2Mo2O2(μ‐S)2Ag2(dppm)2]·4CH3OH·DMF (2, edt = 1,2‐ethanedithiolate dianion, dppm = bis(diphenylphosphino)methane, DMF = N,N‐dimethylformamide) and [(μ‐Cl)2Ag4(μ3‐Cl)2(dppm)2]·4DMF (3), were generated by combining a dinuclear molybdenum precursor [Et4N]2[(edt)2Mo2S2(μ‐S)2] (1a) with two equimolar AgCl and dppm in a CH3OH‐DMF mixed solution. Treatment of complex 1a with one equimolar AgCl and DPEPhos in CH3OH and DMF mixed solutions, producing complex [Et4N][(edt)2Mo2S2(μ‐S)2Ag(DPEPhos)]·CH3OH (4, DPEPhos = bis(2‐diphenylphosphinophenyl)ether). Treatment of complex [nPr4N]2[(edt)2Mo2S2(μ‐S)2] (1b) with AgBr in acetonitrile followed by addition of (NH4)2S produced a dodecanuclear Mo–Ag–S cage cluster [nPr4N]2[{Mo2Ag2S2O2(edt)2}3(μ6‐S)]·1.5CH3CN (5). Complexes 2−5 have been characterized by infrared(IR), 1H NMR, UV‐vis, and fluorescence spectroscopies. Moreover, molecular structures of complexes 2−5 have been established by single‐crystal X‐ray crystallography. Addition of [(edt)2Mo2O2(μ‐S)2]2− with AgCl or AgBr in the presence of dppm, DPEPhos or (NH4)2S produces three Mo/S/Ag cluster complexes [(edt)2Mo2O2(μ‐S)2Ag2(dppm)2], [Et4N][(edt)2Mo2S2(μ‐S)2Ag(DPEPhos), and [nPr4N]2[{Mo2Ag2S2O2(edt)2}3(μ6‐S)], suggests that the strong donor ligand, such as dppm, DPEPhos, and S2− could promote the formation of multinuclear heterometallic cluster complexes.