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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2004, 3403 - 3407, DOI: 10.1039/B411313F

Stoichiometric reactions of methylparathion with a palladium aryl oxime metallacycle

Mieock Kim and François P. Gabbaï

The reaction of [Pd3(OAc)6] with (E)-acetophenone oxime and pyridine in CHCl3 under reflux affords the metallacycle [Pd(OAc){C,N-(C6H4C(CH3)NOH)-2}(py)]( 1) as a yellow air-stable complex. The same reaction carried out at room temperature in the absence of pyridine affords the trinuclear oximato complex [Pd(µ-(E)-ONC(CH3)Ph)(µ-OAc)]3( 2), which can be converted into 1 upon heating in the presence of pyridine. As indicated by 1H and 31P NMR spectroscopy, complex 1 reacts with methylparathion in acetone-d6–D2O solutions to afford [Pd(SP(O)(OCH3)2){C,N-(C6H4C(CH3)NOH)-2}(py)]( 3) and [Pd(µ-SP(O)(OCH3)2){C,N-(C6H4C(CH3)NOH)-2}]2( 4) as well as free p-nitrophenol. Compounds 1– 4 have been characterized by single-crystal X-ray analysis, NMR and EA. Compounds 1 and 3 are mononuclear complexes with the acetate and dimethylthiophosphate ligand, respectively, trans from the phenyl group. Compound 2 is a trinuclear complex whose structure can be derived from that of [Pd3(OAc)6] by replacing three of the acetate ligands on one side of Pd3 plane by three N,O-coordinated oximate ligands. Complex 4 is a dinuclear complex in which the two square-planar palladium moieties are linked by the sulfur atoms of the bridging dimethylthiophosphate ligands.

Graphical abstract image for this article (ID: B411313F)