Abstract
N-(2-Thienyl)pyrazole (H(2-tpz)) gives the pyrazole- N-coordinated complex [PdCl 2(H(2-tpz)) 2] with palladium(II) chloride and N-(3-thienyl)pyrazole (H(3-tpz)) gives similarly [PdCl 2(H(3-tpz)) 2] and cyclopalladated [PdCl(3-tpz)] 2. The cyclopalladation occurs mainly at position 2 of the thiophene ring with a significant amount of the reaction at position 4 (ratio 3 : 1), contrary to lithiation which is reported to occur exclusively at position 2. H(3-tpz) is also metallated similarly by hexachlorotetrakis(tri-n-butylphosphine)dirhodium(III) to give [RhCl 2(PBu 3)(3-tpz)] 2. These dimeric palladium and rhodium complexes form adducts with pyridine and tri-n-butylphosphine.
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