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首页> 外文期刊>Chemistry: A European journal >The Role of Solvent on the Mechanism of Proton Transfer to Hydride Complexes: The Case of the [W3PdS4H3ACHTUNGTRENUNG(dmpe)3(CO)]+ Cubane Cluster
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The Role of Solvent on the Mechanism of Proton Transfer to Hydride Complexes: The Case of the [W3PdS4H3ACHTUNGTRENUNG(dmpe)3(CO)]+ Cubane Cluster

机译：溶剂在质子转移至氢化物络合物中的作用：[W3PdS4H3ACHTUNGTRENUNG（dmpe）3（CO）] +古巴族团簇的案例

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摘要

The kinetics of reaction of the [W3PdS4H3ACHTUNGTRENUNG(dmpe)3(CO)]+ hydride cluster (1+) with HCl has been measured in dichloromethane, and a second-order dependence with respect to the acid is found for the initial step. In the presence of added BF4 the second-order dependence is maintained, but there is a deceleration that becomes more evident as the acid concentration increases. DFT calculations indicate that these results can be rationalized on the basis of the mechanism previously proposed for the same reaction of the closely related [W3S4H3- ACHTUNGTRENUNG(dmpe)3]+ cluster, which involves parallel first- and second-order pathways in which the coordinated hydride interacts with one and two acid molecules, and ion pairing to BF4 hinders formation of dihydrogen bonded adducts able to evolve to the products of proton transfer. Additional DFT calculations are reported to understand the behavior of the cluster in neat acetonitrile and acetonitrile–water mixtures. The interaction of the HCl molecule with CH3CN is stronger than the W H···HCl dihydrogen bond and so the reaction pathways operating in dichloromethane become inefficient, in agreement with the lack of reaction between 1+ and HCl in neat acetonitrile. However, the attacking species in acetonitrile– water mixtures is the solvated proton, and DFT calculations indicate that the reaction can then go through pathways involving solvent attack to the W centers, while still maintaining the coordinated hydride, which is made possible by the capability of the cluster to undergo structural changes in its core.
机译：在二氯甲烷中测量了[W3PdS4H3ACHTUNGTRENUNG（dmpe）3（CO）] +氢化物簇（1+）与HCl的反应动力学，并且在初始步骤中发现了相对于酸的第二级依赖性。在添加BF 4的情况下，维持了二阶依赖性，但是随着酸浓度的增加，减速作用变得更加明显。 DFT计算表明，可以根据先前提出的与密切相关的[W3S4H3- ACHTUNGTRENUNG（dmpe）3] +簇相同反应的机理对这些结果进行合理化，其中涉及平行的一阶和二阶途径，其中配位的氢化物与一个和两个酸分子相互作用，并且与BF4的离子配对阻碍了能够发展为质子转移产物的二氢键加合物的形成。据报道，通过额外的DFT计算可以了解簇在纯乙腈和乙腈-水混合物中的行为。 HCl分子与CH3CN的相互作用强于W H···HCl二氢键，因此在二氯甲烷中操作的反应路径效率低下，这与纯乙腈中1+和HCl之间没有反应的情况相一致。但是，乙腈-水混合物中的攻击物质是溶剂化的质子，DFT计算表明该反应可以通过涉及溶剂攻击W中心的途径，同时仍保持配位氢化物，这是由于集群的核心结构发生变化。

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