Reactions of the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having nonequivalent two platinum atoms, Pt(N2O2) and Pt(N4), with p-styrenesulfonate, 2-methyl-2-propene-1-sulfonate, 4-penten-1-ol, and 4-pentyn-ol were studied kinetically. Under the pseudo first-order reaction conditions that the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed: the olefin π-coordinates preferentially to the Pt(N2O2) in the first step (step 1), followed by the second π-coordination of another olefin molecule to the Pt(N4) (step 2). In the next step (step 3), the nucleophilic attack of water to the coordinated olefin triggers the π-σ bond conversion on the Pt(N2O2), and the second π-bonding olefin molecule on the Pt(N4) is released. Finally, reductive elimination occurs to the alkyl group on the Pt(N2O2) to produce the alkyl compound (step 4). The first water substitution with olefin (step 1) occurs to the diaqua and aquahydroxo forms of the complex, whereas the second substitution (step 2) proceeds either on the coordinated OH-on the Pt(N4) (path a) or on the coordinatively unsaturated five-coordinate intermediate of the Pt(N4) (path b), in addition to the common substitution of H2O (path c). The reactions of p-styrenesulfonate and 2-methyl-2-propene-1-sulfonate proceed through paths b and c, whereas the reactions of 4-penten-1-ol and 4-pentyn-1-ol proceed through paths a and c. This difference reflects the difference of the trans effect and/or trans influence of the π-coordinated olefins on the Pt(N2O2). The pentacoordinate state in path b is employed only by the sulfo-olefins, because these exert stronger trans effect. The steps 3 and 4 reflect the effect of the axial alkyl ligand (R) on the charge localization R-PtIV(N2O2)-PtII (N4))and delocalization (R-PtIII(N2O2)-PtIII (N4)(N4)-OH2); when R is p-styrenesulfonate having an electron withdrawing group, the charge localization in the dimer is less pronounced and the water molecule on the Pt(N4) atom is retained (RPtIII(N2O2)-PtIII (N4)-OH2) in the intermediate state. In both routes, the alkyl group undergoes nucleophilic attack of water, and the oxidized products are released via reductive elimination.
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