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    • Oxidation of phosphine by sulfur or selenium involving a catalytic cycle in the interconversion of monomer and tetramer forms of copper-maleonitriledithiolate complexes

      Biplab K Maiti Sabyasachi Sarkar

      Full Papers Volume 121 Issue 1 January 2009 pp 37-41

    • Fulltext

       

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      Permanent link:
      https://www.ias.ac.in/article/fulltext/jcsc/121/01/0037-0041

    • Keywords

       

      Monomer $\leftrightarrow$ tetramer interconversion; catalytic cycle; phosphine oxidation reduction; sulfur; selenium.

    • Abstract

       

      The addition of triphenylphosphine (PPh3), into [Et4N]4[Cu4(mnt)4] shifted its characteristic electronic spectral band at 377 nm to 372 nm which is identical to that of the monomeric species, [Et4N][Cu(mnt)(PPh3)]. This reaction was followed by electrochemical study and also by 31P NMR spectroscopy. Such interconversion with the participation of breaking of bridging copper-$\mu_3$-sulfur bond with the formation of new copper-phosphorous bond led to the development of a catalytic cycle using excess PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S was found to be $0.8 \times 10^{-2} s^{-1}$ and that with Se was $0.6 \times 10^{-2} s^{-1}$ using this catalytic system.

    • Author Affiliations

       

      Biplab K Maiti1 Sabyasachi Sarkar1

      1. Department of Chemistry, Indian Institute of Technology, Kanpur 208 016

    • Dates

       
      Published
      January 2009
      Manuscript received
      11 August 2008
      Manuscript revised
      6 September 2008

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