Copper bis(thiosemicarbazone) Complexes with Pendent Polyamines: Effects of Proton Relays and Charged Moieties on Electrocatalytic HER
Copper bis(thiosemicarbazone) Complexes with Pendent Polyamines: Effects of Proton Relays and Charged Moieties on Electrocatalytic HER
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DOI：
10.1002/ejic.202000774
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发表时间：
2020-12-23
影响因子：
2.3
通讯作者：
Grapperhaus, Craig A.
中科院分区：
文献类型：
--
作者：
Calvary, Caleb A.;Hietsoi, Oleksandr;Grapperhaus, Craig A.
一系列新的bis（氨基硫脲基）Cu（II）与侧链多胺、二乙酰基-（N，-二甲基乙二胺硫代氨基脲）-（N '-甲基-3-氨基硫脲基）丁烷-2，3-二亚胺）-铜（II）（Cu-1），二乙酰基-双（N-二甲基亚乙基二氨基-3-氨基硫脲基）丁烷-2，3-二亚胺）-铜（II）（Cu-3）及其阳离子衍生物Cu-2和Cu-4，已合成和充分的光谱，电化学和X-射线衍射方法的特点。配合物Cu-1-Cu-4是Cu（ATSM）的类似物，其含有类似的具有末端非配位胺的N2 S2供体核。用N，N-二甲基乙二胺取代H（2）ATSM的末端胺的甲基，然后烷基化，在配体骨架中产生带电荷的季胺。带电的网站调谐的氧化还原电位的配合物，其物理和电子性质的变化最小。所有四种铜配合物的HER活性在乙腈与冰乙酸中进行评价。所有配合物的HER过电位均低于Cu（ATSM），这归因于电荷效应。Cu-1和Cu-3的侧基胺具有最低的HER超电势，因为侧基叔胺还充当质子中继以增强催化条件下的质子重排。配合物Cu-3表现出最高的活性，TOF为12 × 10（3）s（-1），过电位为0.65 V，法拉第效率为100%。
A series of new bis(thiosemicarbazonato) Cu(II) complexes with pendent polyamines, diacetyl-(N, -dimethylethylenediaminothiosemicarbazonato)-(N'-methyl-3-thio-semicarbazonato)butane-2,3-diimine)-copper(II) (Cu-1), diacetyl-bis(N-dimethylethylenediamino-3-thiosemicarbazonato)butane-2,3-diimine)-copper(II) (Cu-3), and their cationic derivatives Cu-2 and Cu-4, have been synthesized and fully characterized by spectroscopic, electrochemical, and X-ray diffraction methods. Complexes Cu-1-Cu-4 are analogues of Cu(ATSM), which contains a similar N2S2 donor core with terminal non-coordinating amines. Substitution of the methyl group(s) of the terminal amines of H(2)ATSM with N,N-dimethylethylenediamine followed by alkylation generates a charged quaternary amine in the ligand framework. The charged site tunes the redox potentials of the complexes with minimal changes in their physical and electronic properties. The HER activity of all four copper complexes were evaluated in acetonitrile with glacial acetic acid. All of the complexes have lower HER overpotentials than Cu(ATSM), which is attributed to charge effects. The pendent amines of Cu-1 and Cu-3 have the lowest HER overpotential as the pendent tertiary amine also serves as a proton relay to enhance proton rearrangement under catalytic conditions. Complex Cu-3 showed the highest activity with a TOF of 12 x 10(3) s(-1), an overpotential of 0.65 V, and faradaic efficiency of 100 %.