Synthesis and Electrocatalytic Property of Diiron Hydride Complexes Derived from a Thiolate-Bridged Diiron Complex

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• 作者：Dawei Yang ; Yang Li ; Baomin Wang ; Xiangyu Zhao ; Linan Su ; Si Chen ; Peng Tong ; Yi Luo ; Jingping Qu
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：November 2, 2015
• 年：2015
• 卷：54
• 期：21
• 页码：10243-10249
• 全文大小：424K
• ISSN：1520-510X

文摘

Interaction of a diiron thiolate-bridged complex, [Cp*Fe(渭-畏²:畏⁴-bdt)FeCp*] (1) (Cp* = 畏⁵-C₅Me₅; bdt = benzene-1,2-dithiolate) with a proton gives an Fe^IIIFe^III hydride bridged complex, [Cp*Fe(渭-bdt)(渭-H)FeCp*][BF₄] (3[BF₄]). According to in situ variable temperature ¹H NMR studies, the formation of 3[BF₄] was evidenced to occur through a stepwise pathway: protonation occurring at an iron center to produce terminal hydride [Cp*Fe(渭-bdt)(t-H)FeCp*][BF₄] (2) and subsequent intramolecular isomerization to bridging hydride 3[BF₄]. A one-electron reduction of 3[BF₄] by CoCp₂ affords a paramagnetic mixed-valent Fe^IIFe^III hydride complex, [Cp*Fe(渭-畏²:畏²-bdt)(渭-H)FeCp*] (4). Further, studies on protonation processes of diruthenium and iron鈥搑uthenium analogues of 1, [Cp*M1(渭-bdt)M2Cp*] (M1 = M2 = Ru, 5; M1 = Fe, M2 = Ru, 8), provide experimental evidence for terminal hydride species at these bdt systems. Importantly, diiron or diruthenium hydride bridged complexes 3[BF₄], 7[BF₄] and iron鈥搑uthenium heterodinuclear complex 8[PF₆] can realize electrocatalytic hydrogen evolution.