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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Mechanisms of reactions of dihydrogen complexes: Formation of trans-[RuH(H-2)(dppe)(2)](+) and substitution of coordinated dihydrogen
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Mechanisms of reactions of dihydrogen complexes: Formation of trans-[RuH(H-2)(dppe)(2)](+) and substitution of coordinated dihydrogen

机译：二氢配合物的反应机理：反式[RuH（H-2）（dppe）（2）]（+）的形成和配位二氢的取代

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The reactions between cis-[RuH2(DPPE)(2)] and a number of acids in THF solution (DPPE = Ph2PCH2CH2PPh2) show biphasic kinetics, with initial formation of trans-[RuH(H-2)(DPPE)(2)](+) followed by slower substitution of coordinated dihydrogen by the anion of the acid. The formation of the dihydrogen complex is a second-order process that occurs with an inverse kinetic isotope effect and rate constants k(HX) strongly dependent on the nature of the acid. There is a linear correlation between the values of log k(HX) for cis-[RuH2(DPPE)(2)] and the related cis-[FeH2(PP3)] [PP3 = P(CH2CH2PPh2)(3)] that leads to two parameters, S and R, that can be used as a measure of the selectivity and intrinsic reactivity of the dihydride toward acids. The possible contributions to the values of these parameters are discussed, especially the role of the isomerization of the starting complex and the basicity of the reacting species. The substitution of coordinated dihydrogen in trans-[RuH(H-2)(DPPE)(2)](+) occurs through a simple dissociative mechanism instead of the more complicated one previously proposed far substitutions in the analogous Fe complex; the mechanistic change is associated with the relative strength of the M-H-2 and M-P(chelate) bonds. [References: 42]
机译：顺式[[RuH2（DPPE）（2）]]与许多酸在THF溶液中的反应（DPPE = Ph2PCH2CH2PPh2）显示出两相动力学，最初形成了反式[RuH（H-2）（DPPE）（2） ]（+），然后由酸的阴离子缓慢取代配位二氢。二氢配合物的形成是第二级过程，发生时具有逆动力学同位素效应，速率常数k（HX）强烈依赖于酸的性质。顺式[RuH2（DPPE）（2）]的log k（HX）值与相关的顺式[FeH2（PP3）] [PP3 = P（CH2CH2PPh2）（3）]之间存在线性关系S和R这两个参数，可以用来衡量二氢化物对酸的选择性和固有反应性。讨论了对这些参数值的可能贡献，特别是起始配合物异构化的作用和反应物种的碱性。反式-[RuH（H-2）（DPPE）（2）]（+）中的配位二氢取代是通过一种简单的解离机理发生的，而不是通过类似的Fe络合物中较早提出的远取代来实现的。机械变化与M-H-2和M-P（螯合物）键的相对强度有关。 [参考：42]

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