High pressure cyanide exchange study on a square-planar tetracyanometalate complex of Pt(II)

被引：1

作者：

Monlien, FJ ^{[1
]}

Abou-Hamdan, A ^{[1
]}

Helm, L ^{[1
]}

Merbach, AE ^{[1
]}

机构：

[1] Univ Lausanne, Inst Chim Minerale & Analyt, CH-1015 Lausanne, Switzerland

来源：

HIGH PRESSURE RESEARCH | 2000年 / 18卷 / 1-6期

关键词：

platinum; cyanide exchange kinetics; high pressure NMR; activation volume;

D O I：

10.1080/08957950008200986

中图分类号：

O4 [物理学];

学科分类号：

0702 ;

摘要：

Previous studies of cyanide exchange on square planar tetracyanoplatinate complex [Pt(CN)(4)](2-) have been undertaken only at a high pH. For a more complete Fundamental understanding of this system we extended the investigations of these exchanges over a large pH range, NMR kinetics methods (magnetisation transfer, isotopic exchange) proved to be very useful for obtaining quantitative rate data of the cyanide exchange on this complex. In fact it is quite significant that the reactivity of this metal center spans a ca, 9-order of magnitude range as a function of pH. Variable temperature and variable pressure studies were undertaken in aqueous solutions and the following activation parameters obtained: DeltaH(double dagger) = (25.1 +/- 0.4) kJmol(-1) and activation entropy DeltaS(double dagger)=-(142+/-2) JK(-1)mol(-1) and activation volume DeltaV(double dagger)=-(27+/-2) cm(3)mol(-1).

引用

页码：319 / 324

页数：6

共 16 条

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