Reversible, metal-free hydrogen activation
Reversible, metal-free hydrogen activation
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DOI：
10.1126/science.1134230
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发表时间：
2006-11-17
期刊：
影响因子：
56.9
通讯作者：
Stephan, Douglas W.
中科院分区：
文献类型：
--
作者：
Welch, Gregory C.;Juan, Ronan R. San;Stephan, Douglas W.
尽管氢分子 (H-2) 的可逆共价活化是过渡金属中心的常见反应，但已证明在较轻元素的化合物中难以实现。我们报道了化合物 (C6H2Me3)(2)PH(C6F4) BH(C6F5)(2) (Me，甲基)，该化合物是通过涉及三（五氟苯基）硼烷的仲碳上的二三甲苯基膦取代的不寻常反应而衍生的，在高于 100 摄氏度的温度下会干净地失去 H-2。初步动力学研究表明该过程是一级过程。值得注意的是，脱氢产物 (C6H2Me3)(2)P(C6F4)B(C6F5)(2) 很稳定，并在 25℃ 下与 1 个大气压的 H-2 反应，重新形成起始络合物。还进行了氘化研究来探讨其机制。
Although reversible covalent activation of molecular hydrogen (H-2) is a common reaction at transition metal centers, it has proven elusive in compounds of the lighter elements. We report that the compound (C6H2Me3)(2)PH(C6F4) BH(C6F5)(2) (Me, methyl), which we derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris( pentafluorophenyl) borane, cleanly loses H-2 at temperatures above 100 degrees C. Preliminary kinetic studies reveal this process to be first order. Remarkably, the dehydrogenated product (C6H2Me3)(2)P(C6F4)B(C6F5)(2) is stable and reacts with 1 atmosphere of H-2 at 25 degrees C to reform the starting complex. Deuteration studies were also carried out to probe the mechanism.