Comparison of Cobalt and Nickel Complexes with Sterically Demanding Cyclic Diphosphine Ligands: Electrocatalytic H2 Production by [Co(PtBu2NPh2)(CH3CN)3](BF4)2†
Comparison of Cobalt and Nickel Complexes with Sterically Demanding Cyclic Diphosphine Ligands: Electrocatalytic H2 Production by [Co(PtBu2NPh2)(CH3CN)3](BF4)2†
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钴和镍配合物与空间要求环状二膦配体的比较：[Co(PtBu2NPh2)(CH3CN)3](BF4)2† 电催化生产 H2
DOI：
10.1021/om100395r
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发表时间：
2010
期刊：
影响因子：
2.8
通讯作者：
D. Dubois
中科院分区：
文献类型：
--
作者：
Eric S. Wiedner;Jenny Y. Yang;W. Dougherty;W. Kassel;R. Bullock;M. Dubois;D. Dubois
合成了环状二膦配体 PtBu2NPh2 和 PtBu2NBz2，并用于制备新型 Co(II) 和 Ni(II) 配合物，其化学式为 [M(PtBu2NR2)(CH3CN)n](BF4)2 (n = 2, 3)。通过变温 NMR 数据、X 射线衍射研究和循环伏安法对产品进行了表征，并将新配合物的性质与先前研究的含有 PPh2NR2 配体的配合物的性质进行了比较。这些配体中磷或氮取代基的变化可能导致金属配合物的结构、电化学和反应性显着差异。研究发现，[Co(PtBu2NPh2)(CH3CN)3](BF4)2 是一种有效的电催化剂，可使用四氟硼酸溴苯胺作为酸形成氢气，其转换频率为 160 s−1，过电势为 160 mV。这些钴衍生物是一类有前途的催化剂，有待进一步研究和优化。
The cyclic diphosphine ligands PtBu2NPh2 and PtBu2NBz2 have been synthesized and used to prepare new complexes of Co(II) and Ni(II) with the formula [M(PtBu2NR2)(CH3CN)n](BF4)2 (n = 2, 3). The products have been characterized by variable-temperature NMR data, X-ray diffraction studies, and cyclic voltammetry, and properties of the new complexes have been compared with those of previously studied complexes containing PPh2NR2 ligands. The variation of either phosphorus or nitrogen substituents in these ligands can result in significant differences in the structure, electrochemistry, and reactivity of the metal complexes. [Co(PtBu2NPh2)(CH3CN)3](BF4)2 is found to be an effective electrocatalyst for the formation of hydrogen using bromoanilinium tetrafluoroborate as the acid, with a turnover frequency of 160 s−1 and an overpotential of 160 mV. These cobalt derivatives are a promising class of catalysts for further study and optimization.