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- W2016619571 abstract "Abstract The reaction of the known complex cis , cis ‐[Me 2 Pt a (μ‐dppm)(μ‐SMe 2 )Pt b –CH 2 (CH 2 ) 2 C c H 2 ( Pt b –C c )] [dppm = bis(diphenylphosphanyl)methane] with phthalazine (NN) proceeded by replacement of the labile bridging SMe 2 ligand with the bidentate N‐donor ligand NN to give cis , cis ‐[Me 2 Pt a (μ‐dppm)(μ‐NN)Pt b –CH 2 (CH 2 ) 2 C c H 2 ( Pt b –C c )] ( 1 ) as a pale red solid in good yield. The complex was fully characterized by multinuclear ( 1 H, 31 P, 195 Pt) NMR spectroscopy. The subsequent reaction of complex 1 with excess MeI gave the colorless diplatinum(IV) complex [Me 3 Pt a (μ‐dppm)(μ‐I) 2 Pt b {CH 2 (CH 2 ) 2 C c H 2 ( Pt b –C c )}Me], in which the bridging NN ligand is replaced by bridging iodido ligands. The reddish color of complex 1 , which is due to a metal‐to‐ligand charge transfer (MLCT) band in the visible region, was used to monitor its reaction with MeI in the solvents acetone, CH 2 Cl 2 , and benzene. The kinetic data revealed that the reactions in nonpolar benzene or slightly polar CH 2 Cl 2 proceeded in two steps, each following a common S N 2 mechanism. In the first step, MeI attacked the platina(II)cyclopentane center rather than the dimethylplatinum(II) center, because the first center is more electron‐rich than the second center. In the more polar acetone, the reaction proceeded similarly, with the exception that each step was accompanied by a solvolytic reaction, which was suggested to be responsible for the unusually slower reaction rate in acetone than in benzene or CH 2 Cl 2 . Consistently, the reaction rate in the highly polar solvent CH 3 CN was too slow for any meaningful measurement.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)" @default.
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- W2016619571 date "2008-11-01" @default.
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- W2016619571 title "Uncommon Solvent Effect in Oxidative Addition of MeI to a New Dinuclear Platinum Complex Containing a Platina(II)cyclopentane Moiety" @default.
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- W2016619571 doi "https://doi.org/10.1002/ejic.200800637" @default.
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