ABSTRACT
Reactions of the head-to-tail alpha-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having equivalent two platinum atoms, Pt(N(3)O), with p-styrenesulfonate and 4-penten-1-ol were studied kinetically. Under the pseudo first-order reaction conditions in which the concentration of the Pt(III) dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed for the reaction with p-styrenesulfonate, but for the reaction with 4-penten-1-ol, the reaction was three step. The olefin pi-coordinates to one of the two equivalent Pt atoms in the first step (step 1), followed by the second pi-coordination of another olefin molecule to the other Pt atom (step 2). In the next step (step 3), the nucleophilic attack of water to the first pi-coordinated olefin initiates its pi-sigma bond conversion on the Pt atom, and the second pi-bonding olefin molecule on the other Pt atom is released. Finally, dissociation of the alkyl group on the Pt(N(3)O) and reduction of the Pt(III) dinuclear complex to the Pt(II) dinuclear complex occur (step 4). The first water substitution with olefin (step 1) consists of two paths, the reaction of the diaqua dimer complex (path a) and the reaction of the aquahydroxo dimer complex (path b), whereas the second substitution (step 2) proceeds through three reaction paths: the normal path of the direct substitution of H(2)O (path c), the path of the coordinated OH(-) substitution (path d), and the path via the coordinatively unsaturated five-coordinate intermediate (path e). The reaction with p-styrenesulfonate proceeds through paths c, d, and e, whereas the reaction with 4-penten-1-ol proceeds through paths c and d. The third step (step 3) for the reaction with p-styrenesulfonate involves the coordinatively unsaturated intermediate, but that for the 4-pentene reaction does not. The reactivities of the HH dimer and HT dimer with olefins are compared and discussed.
ABSTRACT
Reactions of the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having nonequivalent two platinum atoms, Pt(N(2)O(2)) and Pt(N(4)), with p-styrenesulfonate, 2-methyl-2-propene-1-sulfonate, 4-penten-1-ol, and 4-pentyn-1-ol were studied kinetically. Under the pseudo first-order reaction conditions that the concentration of the Pt(III) dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed: the olefin pi-coordinates preferentially to the Pt(N(2)O(2)) in the first step (step 1), followed by the second pi-coordination of another olefin molecule to the Pt(N(4)) (step 2). In the next step (step 3), the nucleophilic attack of water to the coordinated olefin triggers the pi-sigma bond conversion on the Pt(N(2)O(2)), and the second pi-bonding olefin molecule on the Pt(N(4)) is released. Finally, reductive elimination occurs to the alkyl group on the Pt(N(2)O(2)) 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(N(4)) (path a) or on the coordinatively unsaturated five-coordinate intermediate of the Pt(N(4)) (path b), in addition to the common substitution of H(2)O (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 pi-coordinated olefins on the Pt(N(2)O(2)). 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-Pt(IV)(N(2)O(2))-Pt(II)(N(4))) and delocalization (R-Pt(III)(N(2)O(2))-Pt(III)(N(4))-OH(2)); 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(N(4)) atom is retained (R-Pt(III)(N(2)O(2))-Pt(III)(N(4))-OH(2)) in the intermediate state. In both routes, the alkyl group undergoes nucleophilic attack of water, and the oxidized products are released via reductive elimination.
