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Solvothermal heterocyclic disulfide/CuX2 (X = Cl, ClO4) reactions involving dynamic S–S and C–S bond cleavage

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Abstract

Under different solvothermal conditions, the reactions of 2-ppds (2-ppds = di[4-(pyridin-2-yl)pyrimidinyl]disulfide) with CuX2 (X = ClO4 or Cl) produced markedly different results because of diverse in situ reactions of 2-ppds involving dynamic S–S and C–S bond cleavage. At 90 °C, reaction of 2-ppds with Cu(ClO4)2 in CH3CN–CH2Cl2-mixed solvent yielded a discrete mononuclear complex, [Cu(L1)2(ClO4)]ClO4 (1), in which 2-ppds was converted into a zwitterion of L1 (L1 = 4-(pyridin-2-yl)pyrimidin-2-ol) involving C–S bond scission followed by attack of water. At 120 °C in DMF–MeOH solvent, reaction of 2-ppds with Cu(ClO4)2 resulted in transformation to L2 (L2 = 4-(pyridin-2-yl)pyrimidine-2-thiolate) through reductive cleavage of the S–S bond concurrent with reduction of Cu2+ to Cu+, leading to the formation of a single tetranuclear coordination complex, [Cu4(L2)4] (2), that comprises a unique Cu4S4 cluster. When the reaction between 2-ppds and CuCl2 was carried out at 90 °C in CH3CN–H2O solvent, a discrete coordination complex, [Cu(L3)(H2O)Cl]Cl (3), was obtained, resulting from conversion of 2-ppds into L3 (L3 = bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane) through extrusion of one S atom from the S–S bond.

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Acknowledgments

We are grateful for the financial support from National Natural Science Foundation of China (NSFC) (Nos. 21171036 and 20801011) and the Fundamental Research Funds for the Central Universities (No. 3207045415).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, China

    Hai-Bin Zhu

  2. Department of Chemical and Pharmaceutical Engineering, Southeast University ChengXian College, Nanjing, 210088, China

    Gang Yao

  3. Jiangsu Zhongbang Pharmaceutical Co., Ltd., Nanjing, 211300, China

    Wei-Si Li

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  1. Hai-Bin Zhu
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  2. Gang Yao
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  3. Wei-Si Li
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Correspondence to Hai-Bin Zhu.

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Zhu, HB., Yao, G. & Li, WS. Solvothermal heterocyclic disulfide/CuX2 (X = Cl, ClO4) reactions involving dynamic S–S and C–S bond cleavage. Transition Met Chem 41, 57–63 (2016). https://doi.org/10.1007/s11243-015-9996-0

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