Trans-dichlorodiammineplatinum(II). Acid hydrolysis and the isotopic exchange of the chloride ligands

Trans-dichlorodiammineplatinum(II). Acid hydrolysis and the isotopic exchange of the chloride ligands
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反式二氯二氨铂(II)。

DOI:
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发表时间:
1961
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通讯作者:
D. Martin
D. Martin
中科院分区:
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文献类型:
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作者:
J. W. Reishus;D. Martin

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顺式stapt (NH/sub 3/)/sub 2/Cl/sub 2/!分别在25度和35度下进行研究。对于第一次酸水解,顺式stapt (NH/sub - 3/)/sub - 2/Cl!+ H/sub 2/O生成顺式stapt (NH/sub 3/)/sub 2/Cl(H/sub 2/O)!/sup +/ + Cl/sup -/时,平衡常数K/sub - 1/为3.3 × 10/sup -//sup 3/ mol /l,速率常数K/sub - 1/为2.5 × 10/sup -//sup 5/ sec/sup -//sup 1/ 25时,顺式STAPt(NH/sub 3/)/sub 2/Cl/sub 2/之间没有明显的直接交换!Cl/sup -/。对于第二次酸水解,顺式stapt (NH/sub 3/)/sub 2/Cl(H/sub 2/O)!/sup +/ + H/sub 2/O生成cis- STAPt(NH/sub 3/)/sub 2/(H/sub 2/O)/sub 2/!/sup 2//sup +/ + Cl/sup -/,平衡常数K/sub 2/等于4 × 10/sup -//sup 5/ mol /l。氯化物与顺式stapt (NH/sub 3/)Cl(H/sub 2/O)的交换!发生的速率与氯化物无关,其特征是一级速率常数k/sub 2/ = 3.3 × 10/sup -//sup 5/ sec/sup -//sup 1/在25DE时。看来这种交换也可能仅通过酸水解机制发生。(认证)
The acid hydrolysis of cis-STAPt(NH/sub 3/)/sub 2/Cl/sub 2/! was studied at 25 and 35 deg . For the first acid hydrolysis, cis-STAPt(NH/sub 3/)/sub 2/Cl! + H/sub 2/O yields cis-STAPt(NH/sub 3/)/sub 2/Cl(H/sub 2/O)!/sup +/ + Cl/sup -/ , the equilibrium co nstant, K/sub 1/, is 3.3 x 10/sup -//sup 3/ mole/l and the rate constant, k/sub 1/, is 2.5 x 10/sup -//sup 5/ sec/sup -//sup 1/ at 25 There is no significant direct exchange between the chloride ligands of cis- STAPt(NH/sub 3/)/sub 2/Cl/sub 2/! and Cl/sup -/. For the second acid hydrolysis, cis-STAPt(NH/sub 3/)/sub 2/Cl(H/sub 2/O)!/sup +/ + H/sub 2/O yields cis- STAPt(NH/sub 3/)/sub 2/(H/sub 2/O)/sub 2/!/sup 2//sup +/ + Cl/sup -/, the equi librium constant K/sub 2/ is 4 x 10/sup -//sup 5/ mole/l at 25 deg . The exchange of chloride with cis-STAPt(NH/sub 3/)Cl(H/sub 2/O)! occurs at a rate which is chloride-independent and is characterized by a first order rate constant, k/sub 2/ = 3.3 x 10/sup -//sup 5/ sec/sup -//sup 1/ at 25DE It appears likely that this exchange also occurs by only an acid hydrolysis mechanism. (auth)