The electrochemistry of Os(III) ammines: Part II. Os(NH3)5Cl2+, Os(NH3)5I2+, Os(NH3)63+
作者： Janis Gulens , John A. Page
DOI: 10.1016/S0022-0728(76)80336-1
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摘要: The electrochemistry of Os(NH3)5Cl2+, Os(NH3)5I2+ and Os(NH3)63+ has been examined in aqueous electrolytes by polarography cyclic voltammetry. Each the Os(III) species was found to undergo an initial one-electron reduction step, but Os(II) products were unstable underwent substitution and/or reoxidation. The net process with penta-ammines acid solution a catalytic H+: Download full-size image In buffered acetate pH 5, pseudo 1st order rate constants 103 s−1 for Os(III)Cl 102 Os(III)I evaluated from polarographic limiting currents. In neutral solution, simple could be observed. Polarographic E1/2 values were: Os(III)H2O, −0.97 V; Os(III)I, −1.01 Os(III)Cl, −1.09 Os(III)OH, −1.23 V Os(NH3)6, −1.02 (vs. SCE). With basic there OH− Os(II)X product, giving overall e→.c.e←. over range potential: Os(III)X+e⇌Os(II)XOs(II)X+OH−→kOs(II)OH+X−Os(II)OH−e⇌Os(III)OH Pseudo measured at 11, Os(II)Cl, 0.2 Os(II)I, 0.02 s−1. There also direct evidence redox cross reaction between Os species: Os(III)X+Os(II)OH→Os(II)X+Os(III)OH With Os(NH3)63+, rates reoxidation processes significantly less than those penta-ammines, showed limited stability.
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