Solvation effects on transition metal hydricity.
Solvation effects on transition metal hydricity.
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溶剂化作用对过渡金属水度的影响。
DOI：
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发表时间：
2015
影响因子：
15
通讯作者：
Jenny Y. Yang
中科院分区：
文献类型：
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作者：
C. Tsay;Brooke N. Livesay;S. Ruelas;Jenny Y. Yang
通过实验确定 [HNi(DHMPE)2][BF4] (DHMPE = 1,2-双(二羟甲基膦)乙烷) 的氢化物供给自由能 (氢度) 与氢在乙腈、二甲基亚砜和水中的杂解裂解能分别为 57.4、55.5 和 30.0 kcal/mol。这项工作代表了首次报道的氢度我们的值与氢和甲酸盐的水度之间的比较表明，随着溶剂极性的增加，值的范围变窄。热化学值还揭示了影响从氢生成氢化物并转移到二氧化碳的总体热力学有利性的溶剂化效应，对于整个合成化学中具有氢化物转移步骤的催化剂的设计和反应性具有重要影响。
The free energy of hydride donation (hydricity) for [HNi(DHMPE)2][BF4] (DHMPE = 1,2-bis(dihydroxymethylphosphino)ethane was experimentally determined versus the heterolytic cleavage energy of hydrogen in acetonitrile, dimethyl sulfoxide, and water to be 57.4, 55.5, and 30.0 kcal/mol, respectively. This work represents the first reported hydricity values for a transition metal hydride donor in three different solvents. A comparison between our values and the hydricity of hydrogen and formate reveals a narrowing in the range of values with increasing solvent polarity. The thermochemical values also reveal solvation effects that impact the overall thermodynamic favorability of hydride generation from hydrogen and transfer to carbon dioxide. The quantitative solvation effects described herein have important consequences to the design and reactivity of catalysts for transformations that have hydride transfer steps throughout synthetic chemistry.
三烷基硼烷辅助后过渡金属氢化物还原 CO(2)。
影响因子：
2.8
作者：
Miller,AlexanderJM;Labinger,JayA;Bercaw,JohnE
通讯作者：
Bercaw,JohnE
影响因子：
62.1
作者：
Appel, Aaron M.;Bercaw, John E.;Bocarsly, Andrew B.;Dobbek, Holger;DuBois, Daniel L.;Dupuis, Michel;Ferry, James G.;Fujita, Etsuko;Hille, Russ;Kenis, Paul J. A.;Kerfeld, Cheal A.;Morris, Robert H.;Peden, Charles H. F.;Portis, Archie R.;Ragsdale, Stephen W.;Rauchfuss, Thomas B.;Reek, Joost N. H.;Seefeldt, Lance C.;Thauer, Rudolf K.;Waldrop, Grover L.
通讯作者：
Waldrop, Grover L.