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Published on: March 19, 2020
Polysulfido Chain in Binuclear Zinc(II) Complexes
Kamal Hossain1, Amit Majumdar1
1School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A and 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Abstract:
The synthesis and a detailed reactivity study of a binuclear zinc(II) bis(benzenethiolate) complex, [Zn2(BPMP)(SPh)2]+ (4), and an unprecedented binuclear zinc(II) pentasulfido complex, [Zn2(BPMP)(μ2-S5)]+ (6), are presented. While one-electron oxidation of the coordinated benzenethiolate ligands in 4 by Cp2Fe+ produces diphenyl disulfide and [Zn2(BPMP)(μ2-OH)]2+ (5), a two-electron redox reaction between coordinated benzenethiolate ligands in 4 and elemental S (S8) generated diphenyl disulfide and the binuclear zinc(II) pentasulfido complex 6. Complex 6 features a chelating, dianionic, pentasulfido (S52-) chain and can consume up to a maximum of 3 equiv of PPh3 to generate Ph3PS and 5, while the reaction of 6 with 1 equiv of diphenylphosphinoethane allowed the isolation of [Zn2(BPMP)(μ2-S4)]+ (7). A proteolysis reaction of the coordinated S52- chain in 6 with fluoroboric acid (HBF4), benzoic acid (PhCOOH), and thioacetic acid (MeCOSH) generates the complexes [Zn2(BPMP)(MeCN)2]3+ (1), [Zn2(BPMP)(μ2-PhCOO)2]+ (8), and [Zn2(BPMP)(μ2-SCOMe)2]+ (9), respectively, while the protonated S52- chain liberates S8 and hydrogen sulfide (H2S). Finally, the transfer of the coordinated benzenethiolate ligands in 4 and the S52- chain in 6 to selected organic compounds, namely, PhCH2Br and PhC(O)Cl, for the generation of various organosulfur compounds is demonstrated.
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