Electrochemical and X-ray structural evidence of multiple molybdenum precursor candidates from a reported non-aqueous electrodeposition of molybdenum disulfide

A published report of electrodeposited molybdenum(iv) disulfide microflowers at 100 °C in the ionic liquid N-methyl-N-propylpiperidinium bis(trifluoromethane)sulfonimide (PP13-TFSI) from 1,4-butanedithiol and the concentrated filtrate from a reaction mixture of molybdenum(vi) trioxide and ethylene glycol could not be reproduced reliably, affording numerous uniquely coloured reaction mixtures that precipitated a variety of crystalline molybdenum coordination complexes. Further attempts to use the same two of these filtrates to electrodeposit molybdenum(iv) disulfide from 0.1 M PP13-TFSI in tetrahydrofuran with 1,4-butanedithiol at room temperature were unsuccessful. Various crude reaction mixtures grew crystals of different identity from eight attempts to synthesize the reported molybdenum-precursor. Single crystal X-ray diffraction (SC-XRD) offered insight into a wide range of structural features from four candidate paramagnetic precursor compounds, including a novel organomolybdenum cluster. Electrochemical studies of the various molybdenum-precursor filtrates, ethylene glycol, and 1,4-butanedithiol were conducted in 0.1 M PP13-TFSI in tetrahydrofuran, offering insight into differences between preparations of the molybdenum-precursor and interference between ethylene glycol and 1,4-butanedithiol on platinum working electrodes. Molybdenum(iv) disulfide electrodeposition attempts included cyclic voltammetry and chronoamperometry on platinum and glassy carbon working electrodes, which led to either no deposited material, or molybdenum, carbon, oxygen, and sulfur containing amorphous and non-homogenous deposits, as indicated by SEM-EDS analysis.