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.

Mechanism of ketone and alcohol formations from alkenes and alkynes on the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex

The following successive axial ligand substitution reactions of the head-to-head (HH) 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex ([(H2O)Pt(NH3)2(μ-C5H4NO)2Pt(NH3)2(H2O)]4+) with halide ions X− (X− = Cl− and Br−) to give monohalogeno and dihalogeno complexes were studied kinetically: [(H2O)Pt(NH3)2(μ-C5H4NO)2Pt(NH3)2(H2O)]4++X− →← [(H2O)Pt(NH3)2(μ-C5H4NO)2Pt(NH3)2(X)]3++H2O, [(H2O)Pt(NH3)2(μ-C5H4NO)2Pt(NH3)2(X)]3++X− →← [(X)Pt(NH3)2(μ-C5H4NO)2Pt(NH3)2(X)]2++H2O.The acid dissociation constant (Kh1) of the axial aqua ligand in the HH dimer and the formation constants (K1X and K2X) of the monohalogeno and dihalogeno complexes were determined spectrophotometrically to be −log(Kh1/M) = 1.71 ± 0.04; log(K1Cl/M−1) = 5.93 ± 0.02, log(K2Cl/M−1) = 3.71 ± 0.00 for the reaction with Cl−, and log(K1Br/M−1) = 6.20 ± 0.05, log(K2Br/M−1) = 4.55 ± 0.01 for the reaction with Br−. The two platinum atoms are nonequivalent in the HH dimer, in which the first deprotonation occurs selectively to the water m...

Kinetics and Mechanisms of the Axial Ligand Substitution Reaction of the Head-to-head 2-Pyridonato-bridged cis-Diammineplatinum(III) Dinuclear Complex

Mechanistic studies on monodentate–ligand substitution of five-coordinate trigonal-bipyramidal platinum (II) complexes with tris[2-(diphenylphosphino)ethyl]phosphine

John R. Paxson

Papers

Aquation equilibrium and isotopic exchange of chloride for chloro(diethylenetriamine)platinum(I) chloride

Aquotisierungsgleichgewicht und chloridisotopenaustausch von chloro-(diaethylentriamin)-platin(ii)-chlorid