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Synthesis, Characterization, Electrochemistry and Oxo-transfer Kinetics of Oxomolybdenum-(VI), -(V) and -(IV) Complexes with ONS Donors

DOI: 10.1039/DT9920001357

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Journal of the Chemical Society, Dalton Transactions p. 1357 - 1364 (1992)

Update date:2022-08-04

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Authors:

Bhattacharjee, SamiranBhattacharjee, Samiran

Bhattacharyya, RamgopalBhattacharyya, Ramgopal

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Article abstract of DOI:10.1039/DT9920001357

cis-Dioxomolybdenum(VI) complexes of the type are Mo=O...Mo bridged oligomers.In the presence of donors they are converted into monomeric .When a 5-Cl or 5-Br substituent occurs in the salicyl phenyl ring oligomers are not formed, but besides also are obtained.All these complexes undergo oxo transfer to PPh3 at room temperature, furnishing oxomolybdenum(IV) derivatives, , and PPh3O.The complexes in dmf accepts an oxygen atom from Me2SO, affording and Me2S.The ions (2-) (X=Cl or Br) react with the ligands H2L furnishing thiolato-bridged dimers, , which show sub-normal magnetic moments and EPR spectra typical of an antiferromagnetic material.The MoO2(2+) complexes undergo irreversible electrochemical reduction furnishing oxomolybdenum(V) derivatives at potentials commensurate with the nature of substituent in the salicyl group of the ligand.The molybdenum-(V) and -(IV) complexes also show interesting electrochemical reductive as well as oxidative responses centred on the metal.The oxo transfer from (unsubstituted salicyl ring) to PPh3 occurs in a second-order process with rate constant 1.32*10-2 dm3 mol-1 s-1 at 30 deg C.The oxo transfer from Me2SO to the MoO(2+) core is much faster.The reaction between PPh3 and Me2SO furnishing PPh3O and Me2S becomes highly facile in the presence of as catalyst.

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Product name:Hydrazinecarbodithioic acid, [(2-hydroxy-5-methylphenyl)methylene]-, phenylmethyl ester

Cas No:141950-86-9

141950-86-9

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