| Budget Amount *help |
¥5,400,000 (Direct Cost: ¥5,400,000)
Fiscal Year 1988: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1987: ¥4,400,000 (Direct Cost: ¥4,400,000)
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| Research Abstract |
Dunuclear Pt(II) pr (III) complex, having Pt(N-S)_4Pt core where the N-S represents a substituted pyridine-2-thiolato ligand (Rpyt), exists in four isomers. They are tentatively denoted as cis^-, trans^-, 3S- and 4S-isomers in which the former two have cis-PtS_2N_2 halves while the latter two invole PtS_3N and PtS_4 moieties. Lsolation and characterization have been made for the following 23 complexes: cis^- and trans^-[Pt_2(4-mpyt)_4], cis-[Pt_2X_2(4-mpyt)_4](X=CI,Br,I,CN), trans-[Pt_2X_2(4-mpyt)_4](X=CI,Br,I,CN), 3S-[Pt_2X_2(4-mpyt)_4](X=CI,Br,I,CN),cis-[Pt_2(CN)X(4-mpyt)_4](X=CI,Br,I,N_3), trans-[Pt_2(CN)X(4-mpyt)_4](X=CI,Br,I), 3S-[CN(N_3),I(S_3)]-[Pt_2(CN)I(4-mpyt)_4], 3S-[CN(S_3),I(N_3)]-[Pt_2(CN)I(4-mpyt)_4]. Collection has been made on the^<195>Pr and ^<13>C nmr data of these complexes. The ^<195>Pt chemical shifts are unable to explain in terms of the oxidation state of Pt, donor-atom property and energy separation of ground-excited state giving nonzero magnetic transition moment, indicating strong effect of Pt^<III>--Pt^<III> bonding. Kinetic parameters for cis-[Pt_2X_2(pyt)_4] + CN^--- cis-[Pt_2(CN)X(pyt)_4] + X^-, cis-[Pt_2(CN)X(pyt)_4] + Y^--- cis-[Pt_2(CN)Y(pyt)_4] + X^-, indicate the dissociative mechanism for these substitution reactions. The study for cis-[Pd_2(pyt)_4] dis- closed that the Pd^6+_ dimer is much less stable than the Pt^6+_ counterpart though the former is produced by electrochemical oxidation of the Pd^4+_ complex inpresence of halide ion.
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