6533b82bfe1ef96bd128d564

RESEARCH PRODUCT

Protonation and methylation reactions of 2-pyridyl-palladium(II) and -platinum(II) complexes

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Abstract The reactions of strong acids HX and HClO4 with the 2-pyridyl complexes [PdX(μ-C5H4N-C2,N)(PPh3)]2 (X = Cl, Br), trans-[PdCl(C5H4N-C2)(PEt3)2] and [PdCl(C5H4N-C2)(dppe)] yield the N-protonated derivatives cis-[PdX2-(C5H5N-C2)(PPh3)], trans-[PdCl(C5H5N-C2)(PEt3)2]ClO4 and [PdCl-(C5H5N-C2)(dppe)]ClO4, respectively. The terminal 2-pyridyl group of trans-[PdCl(C5H4N-C2)(PEt3)2] and [PdCl(C5H4N-C2)(dppe)] also reacts with Me2SO4/NaClO4 to give trans-[PdClC5H4(l-Me)N-C2(PEt3)2]ClO4 and [PdClC5H4(l-Me)N-C2(dppe)]ClO4. Analogous N-protonation or N-methylation reactions occur with trans-[PtBr(C5H4N-C2)(L)2] (L = PEt3, PPh3). The complexes trans-[MX(C5H5N-C2)(PMe2Ph)2]ClO4 (M = Pd, X = Cl and Br; M = Pt, X = Br) exhibit restricted rotation of the protonated 2-pyridyl group around the MC bond. This and other chemical results and spectral data, such as the 13C NMR data of the PEt3 derivatives, are interpreted in terms of a significant contribution of a carbene-like limiting structure to the electronic configuration of this new type of ligand.