Effect of Redox Active Ligands on the Electrochemical Properties of Manganese Tricarbonyl Complexes
作者:Benjamin D. Matson、Elizabeth A. McLoughlin、Keith C. Armstrong、Robert M. Waymouth、Ritimukta Sarangi
DOI:10.1021/acs.inorgchem.9b00652
日期:2019.6.3
−1.68 V and −1.89 V vs Fc+/0 in acetonitrile. The key electronic structure differences between 1 and 4 that lead to disparate electrochemical properties are investigated using a combination of Mn–K-edge X-ray absorption spectroscopy (XAS), Mn–Kβ X-ray emission spectroscopy (XES), and density functional theory (DFT) on 1, 4, their debrominated analogues, [Mn(L)(CO)3(CH3CN)][CF3SO3] (L = bipy 2, azpy
报告了中性Mn(azpy)(CO)3(Br)4(azpy = 2-phenylazoazopyridine)配合物的合成,结构表征和电化学行为,并将其与结构类似物Mn(bipy)(CO)3(Br )1(联吡啶= 2,2'-联吡啶)。4所在温和的电位表现出可逆的两电子还原(-0.93相对于Fc + / 0的乙腈溶液)在对比1,其表现出在-1.68伏两连续单电子还原和-1.89相对于Fc + / 0在乙腈。1和4之间的关键电子结构差异其导致不同的电化学特性上使用的Mn-K边缘X-射线吸收光谱的一个组合(XAS),锰KβX射线发射光谱(XES)和密度泛函理论(DFT)研究1,4,它们的脱溴类似物[Mn(L)(CO)3(CH 3 CN)] [CF 3 SO 3 ](L = bipy 2,azpy 5),和两电子还原的对应物[Mn(bipy)(CO)3 ] [K(18-crown-6)] 3和[Mn(azpy)(CO)3