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The kinetics and mechanism of the ligand substitution reaction of aquapentacyanoruthenate(II) with d-penicillamine in aqueous medium
Journal of Chemical Research ( IF 1.0 ) Pub Date : 2020-11-24 , DOI: 10.1177/1747519820961015
Rupal Yadav 1 , Radhey Mohan Naik 1
Affiliation  

The kinetics of the formation of the light orange–coloured complex [Ru(CN)5D-PA]3− are studied spectrophotometrically through substitution of a coordinated H2O molecule in aquapentacyanoruthenate(II) [Ru(CN)5OH2]3− by interaction with D-penicillamine [D-PA] in aqueous medium at 490 nm (λmax of [Ru(CN)5D-PA]3−). The reaction is monitored under pseudo-first-order conditions, taking [D-PA] in excess over [Ru(CN)5OH23−]. The effects of various reaction parameters on the rate of the reaction are investigated. Experimental observations reveal that the variation in [D-PA] obeyed the first-order rate law while it is found to be invariant with [Ru(CN)5OH23−] in the whole experimental range. With ionic strength variation, as the reaction advances a decrease in the reaction rate is noticed. The product stoichiometry is assigned as 1:1. The ease of substitution at an H2O molecule in [Ru(CN)5OH23−] is considered on the basis of the electronic effect generated through interactions of the M–OH2 bond. A provisional mechanism based on the calculated results is proposed based on the slowest step of the reaction.



中文翻译:

水性介质中水合五氰基钌(II)与d-青霉胺配体取代反应的动力学和机理

通过取代水合戊二酸钌(II)[Ru(CN)5 OH 2 ]中配位的H 2 O分子的分光光度法研究了浅橙色络合物[Ru(CN)5 D-PA] 3-的形成动力学。3-通过用d青霉胺相互作用[d-PA]中在490nm(λ水性介质最大的[Ru(CN)的5 d-PA] 3- )。该反应伪一阶条件下监测,取[d-PA]在过量的[Ru(CN)5 OH 2 3-]。研究了各种反应参数对反应速率的影响。实验观察表明,在整个实验范围内,[D-PA]的变化服从一阶速率定律,而[Ru(CN)5 OH 2 3-则是不变的。随着离子强度的变化,随着反应的进行,注意到反应速率的降低。产物化学计量为1:1。根据通过M–OH 2相互作用产生的电子效应,考虑[Ru(CN)5 OH 2 3- ]中H 2 O分子的易取代性键。基于反应最慢的步骤,提出了一种基于计算结果的临时机制。

更新日期:2020-11-26
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