Multinuclear NMR study and crystal structures of complexes of the types cis- and trans-Pt(Ypy) 2X 2, where Ypy=pyridine derivative and X=Cl and I

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Complexes of the types cis- and trans-Pt(Ypy) 2X 2 where Ypy is a methyl derivative of pyridine and X=Cl or I were studied by spectroscopic methods, especially by multinuclear NMR spectroscopy. In 195Pt MNR, the cis-dichloro compounds were observed between −1998 and −2021 ppm in CDCl 3, while the trans compounds were found at slightly lower field, between −1948 and −1973 ppm. The diiodo species were observed at much higher field, between −3199 and −3288 ppm for the cis isomers and between −3122 and −3264 ppm for the trans isomers. In 1H NMR, the 3 J( 195Pt 1H) coupling constants are larger for the cis compounds (about 42 ppm) than for the trans isomers (about 33 ppm). In 13C NMR, the values of 3 J( 195Pt 13C) were also found to be larger for the cis complexes. There seems to be a slight dependence of the p K a values of the protonated ligands on the δ(Pt) chemical shifts. The presence of π-bonding between Pt and the pyridine ligands do not seem very important. The crystal structures of three dichloro and five diiodo complexes were determined, in an attempt to obtain information on the trans influence of the three ligands. The results have shown that the iodo ligand has the greatest trans influence. Chloro and pyridine ligands seem to have similar trans influence, although, the chloro ligand seems to have a slightly larger influence than pyridine derivatives. One structure, trans-Pt(2-pic) 2I 2, has shown a syn conformation of the two 2-picoline ligands.