Abstract
Reactions of 2-(2-pyridyl)benzo[ b]furan (Hpbf), 1-(2-pyridyl)indole(Hpyi) and 1-(2-pyrimidyl)indole (Hpmi) with palladium(II) acetate in refluxing acetonitrile resulted in the formation of unexpected nitro complexes, [Pd(NO 2)L(CH 3CN)](L=pbf, pyi and pmi). The presence of NO 2 in the square planar dimethylsulfoxide(dmso) derivatives, [Pd(NO 2)L(dmso)] (L=pbf and pyi) were confirmed by X-ray analysis. Palladation occurred at the C-3 of pbf and at the C-2 of pyi and pmi and a five member palladacycle was formed. The NO 2 was coordinated trans to the pyridine-N atom and the dmso trans to the C atom through the O atom. Cyclorhodation of Hpbf, Hpyi and Hpmi with trichlorobis(tri- n-butylphosphine)rhodium(III) were similarly occurred inrefluxing toluene to afford octahedral complexes, [RhCl 2L(PBu 3) 2],(PBu 3=tri- n-butylphosphine). The octahedral structure of [RhCl 2(pmi)(PBu 3) 2] was also determined by X-ray analysis. The two PBu 3ligands were coordinated trans to each other and the strong trans influence of the σ-C donor atom stretched one Rh–Cl bond trans to it.
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