분광광도법을 이용하여 [pt[dien]X]$^+$(X = $Cl^-$, $Br^-$, $I^-$) 와 ${NO_2}^-$와의 치환반응을 $20{sim}35^{circ}C,;1{sim}1500$</TEX> bar 범위에서 조사했다. 이들 반응의 속도는 모두 온도와 압력이 증가함에 따라 증가하였고, 치환 용이성은 $Cl^-$ > $Br^-$ > $I^-$였다. 활성화 부피변화(│${Delta}V^{ eq}$│)는 모두 큰 음(-)의 값을 가졌고 온도가 증가함에 따라 감소하였다. $25^{circ}C$에서 구한 일차속도상수($k_1$)와 이차속도상수 ($k_2$)는 압력이 증가함에 따라 다같이 증가하였고, $k_1$ 경로와 $k_2$ 경로에 대한 활성화부피(${Delta}{V_1}^{ eq}$ 와 ${Delta}{V_2}^{ eq}$)는 모두 큰 음(-)의 값을 가졌다. 또한 1 bar에서 $k_1$과 $k_2$를 구했고 온도가 증가함에 따라 모두 증가하였다. 각 반응경로에 대한 활성화파라미터를 결정했고, 모든 실험적 결과로부터 이 반응은 이탈기의 성질과 반응경로에 관계없이 회합(A)메카니즘을 가질 것으로 생각된다.
Kinetics of the substitution reaction of [pt[dien]X]$^+$(X = $Cl^-$, $Br^-$, $I^-$) with NO2- in aqueous solution were investigated by a spectrophotometric method at $20-35^{circ}C$ and 1-1500 bars. The rates of these reactions were increased with raising temperature and pressure. The relative reactivities of replaceable ligands in [pt[dien]X]$^+$ follow the order ($Cl^-$ > $Br^-$ > $I^-$). Activation volumes (${mid}{Delta}V^{ eq}{mid}$) were large negative values and decreased with raising temperature. First ($k_1$) and second($k_2$) order rate constants of these reactions were determined at $25^{circ}C$ and both $k_1$ and $k_2$ were increased with raising pressure and activation volumes (${Delta}{V_1}^{ eq}$, ${Delta}{V_2}^{ eq}$) for the $k_1$ and $k_2$ path were large negative values respectively. The $k_1$ and $k_2$ of these reactions were determined at 1 bar and these values were increased with raising temperature. Activation parameters of $k_1$ and $k_2$ path were determined, therefore it can be inferred frp, these results that the substitution reactions of [pt[dien]X]$^+$ with ${NO_2}^-$ proceed through on associative (A) mechanism independent of a leaving groups and reaction paths.
