Catalysis Letters

, Volume 142, Issue 11, pp 1352-1360

First online:

Selective Oxidation of Nonrefractory and Refractory Sulfides by Cyclopentadienyl Molybdenum Acetylide Complexes as Efficient Catalysts

  • Macchindra G. ChandgudeAffiliated withCatalysis Division, CSIR-National Chemical Laboratory
  • , Ankush V. BiradarAffiliated withCatalysis Division, CSIR-National Chemical Laboratory
  • , Trupti V. KotbagiAffiliated withCatalysis Division, CSIR-National Chemical Laboratory
  • , Vedavati G. PuranikAffiliated withCentre for Material Characterization, CSIR-National Chemical Laboratory
  • , Mohan K. DongareAffiliated withCatalysis Division, CSIR-National Chemical Laboratory
  • , Shubhangi B. UmbarkarAffiliated withCatalysis Division, CSIR-National Chemical Laboratory Email author 

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The synthesis and catalytic properties of molybdenum acetylide complexes CpMo(CO)3(–C≡CR), R = Ph(1), C6H4p-CF3 (2) and C6H4p-CH3 (3) has been studied. The molybdenum acetylide complexes were synthesized from CpMo(CO)3Cl and aryl acetylenes via Stephens–Castro coupling reaction. These complexes were characterized by single crystal X-ray diffraction analysis, FTIR and 1H NMR spectroscopy. These complexes on treatment with hydrogen peroxide, formed corresponding molybdenum oxo-peroxo species. These in situ formed oxo-peroxo species were found very active (up to 100 % conversion) and selective (up to 100 %) oxidation catalysts for various refractory and nonrefractory sulfides. Interestingly, even though the molybdenum acetylide complexes are homogeneous, they could be recycled very efficiently by extracting the catalytically active molybdenum oxo-peroxo species in aqueous phase.

Graphical Abstract

Molybdenum acetylide complexes CpMo(CO)3(C≡CR) synthesized from CpMo(CO)3Cl via Stephens- Castro coupling with aryl acetylenes were used as catalyst precursors for selective oxidation of various sulfides including refractory sulfides to sulfoxides or sulfones using H2O2 as an environmentally benign oxidant with excellent conversion under mild reaction conditions.


Homogeneous catalysis Molybdenum acetylide Refractory sulfide oxidation Oxo-peroxo species