Zhang Xin, Jiang Xuebin, Zhao Qiuting, Li Yongxian, Feng Lei, Ye Shengfa, Tung Chen-Ho, Wang Wenguang
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Inorg Chem. 2024 Jul 29;63(30):14040-14049. doi: 10.1021/acs.inorgchem.4c01783. Epub 2024 Jul 15.
We report two bridging-diazene diiron complexes Cp*Fe(8-quinolinethiolate) () and Cp*Fe(1,2-CyPCHS) (), synthesized by the reaction of hydrazine with the corresponding thiolate-based iron half-sandwich complex, [CpFe(8-quinolinethiolate)] () and CpFe(1,2-CyPCHS) (). Crystallographic analysis reveals that the thiolate sites in and can engage in N-H···S hydrogen bonding with the diazene protons. is thermally stable in both solid and solution states, allowing for one-electron oxidation to afford a cationic diazene radical complex [] at room temperature. In contrast, tends to undergo NH/N transformation, leading to the formation of a Fe(III)-H species by the loss of N. In addition to stabilizing HN=NH species through the hydrogen bonding, the thiolate-based ligands also seem to facilitate proton-coupled electron transfer, thereby promoting N-H cleavage.
我们报道了两种桥连重氮二铁配合物Cp*Fe(8-喹啉硫醇盐) () 和Cp*Fe(1,2-CyPCHS) ()，它们是通过肼与相应的基于硫醇盐的铁半夹心配合物[CpFe(8-喹啉硫醇盐)] () 和CpFe(1,2-CyPCHS) () 反应合成的。晶体学分析表明， 和 中的硫醇盐位点可与重氮质子形成N-H···S氢键。 在固态和溶液状态下均热稳定，在室温下可进行单电子氧化得到阳离子重氮自由基配合物[]。相比之下， 倾向于发生NH/N转化，通过失去N导致形成Fe(III)-H物种。除了通过氢键稳定HN=NH物种外，基于硫醇盐的配体似乎还促进了质子耦合电子转移，从而促进了N-H键的断裂。
