Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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The Study of Rates of Substitution Reaction [Pd(ONN)Cl] ＋ Y$^-\;{\rightleftharpoons}$ [Pd(ONN)Y] + Cl$^-$ (Y = SCN$^-$, CN$^-$, N$_3^-$, Imidazole, Pyridine)

[Pd(ONN)Cl] 착물의 SCN$^-$, CN$^-$, N$_3^-$, Imidazole, Pyridine에 대한 치환반응 속도연구 (제 1 보)

  • Oh Sang-Oh (Department of Chemistry Education, Kyungpook National University) ;
  • Yeo, Hwan Jin (Department of Chemistry Education, Kyungpook National University) ;
  • Cho Iee Yeung (Department of Chemistry Education, Kyungpook National University)
  • 오상오 (경북대학교 자연과학대학 화학과) ;
  • 여환진 (경북대학교 사범대학 화학교육과) ;
  • 조이영 (경북대학교 사범대학 화학교육과)
  • Published : 1991.08.20
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Abstract

Rates of nucleophilic substitution reaction ([Pd (ONN) Cl] + Y$^-\;{\rightleftharpoons}$ [Pd (ONN)Y] + Cl$^-$ ; Y = SCN$^-$, CN$^-$, N$_3^-$, imidazole, pyridine) have been measured in methanol by spectrophotometric method at various temperatures. A set of nucleophilic reactivity constants, n$_{Pd}^{\circ}$ has been calculated. These values show an order of nucleophilicity CN$^-$ > SCN$^-$ > N$_3^-$ > Imidazole > Pyridine. The enthalpy of activation are small positive values and the entropy of activation are large negative values. From these results, it can be inferred that the nucleophilic substitution reaction proceeds through an associative (A) mechanism.

친핵치환반응 ([Pd(ONN)Cl] ＋ Y$^-\;{\rightleftharpoons}$ [Pd(ONN)Y] + Cl$^-$ ; Y = SCN$^-$, CN$^-$, N$_3^-$, imidazole, pyridine)속도를 25 ~ 45$^{\circ}C$ 범위에서 분광광도법으로 측정하였다. 친핵체의 반응성상수, n$_{Pd}^{\circ}$를 계산했으며 그 값은 CN$^-$ > SCN$^-$ > N$_3^-$ > Imidazole > Pyridine의 순서였다. 활성화엔탈피(${\Delta}H^{\neq}$)는 작은 양(+)의 값을, 활성화엔트로피(${\Delta}S^{\neq}$)는 큰 음(-)의 값을 가졌다. 이 결과로 보아 이 착물의 친핵 치환반응은 회합(A) 메카니즘으로 진행됨을 알 수 있었다.

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