The compound [PtMe(bzpy)(DMSO)] (1; bzpy = 2-benzylpyridinate) was synthesized by reaction of cis-[PtMe 2 (DMSO) 2 ] with 1 equiv of bzpyH under reflux conditions in toluene through C-H activation of the carbon-hydrogen bond in 2-benzylpyridine. Then, the complex [PtMe(bzpy)(PPh 3 )], 2, was prepared by addition of PPh 3 to complex 1. Complex 2 undergoes oxidative addition with methyl iodide to give [PtMe 2 I(bzpy)(PPh 3 )], 3. NMR spectroscopy ( 1 H and 31 P), and X-ray crystallography (supported by DFT calculations) clearly showed that the thermodynamic isomer product 3, with iodide trans to C of bzpy rather than the related kinetic isomer, 3, in which iodide is trans to methyl, is obtained. Mechanistic studies using UV-vis spectroscopy and DFT calculations indicate that the reaction occurs by a S N 2 mechanism. The kinetic study of the oxidative addition of methyl iodide to the non-planar, six-membered cyclometalated complex with that of the five-membered cyclometalated [PtMe(ppy)(PPh 3 )], in which ppy = 2-phenylpyridinate, shows that the ring size of the chelating unit has a significant impact on the rate of the reaction.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.