Multielectron Redox Chemistry of Transition Metal Complexes Supported by a Non‐Innocent N
<sub>3</sub>
P
<sub>2</sub>
Ligand: Synthesis, Characterization, and Catalytic Properties
作者:Denan Wang、Danushka M. Ekanayake、Sergey V. Lindeman、Cláudio N. Verani、Adam T. Fiedler
DOI:10.1002/ejic.201800843
日期:2018.10.9
voltammetric studies of each complex, corresponding to MII/MIIIoxidation, LN3P2-based oxidation, and MII/MI reduction (in order of highest to lowest potential). Spectroscopic and computational analyses of 3ox – generated via chemical one-electron oxidation of 3 – revealed that a stable diarylaminyl radical (LN3P2·) is formed upon oxidation. The ability of the CoII complex (2) to function as an electrocatalyst
一种具有 κ5-N,N,N,P,P 螯合能力的新型氧化还原活性二芳基酰胺基配体 (LN3P2) 已被用于制备一系列具有通式 [MII(LN3P2)]X 的配合物,其中 M = Fe (1; X = OTf)、Co (2; X = ClO4) 或 Ni (3; X = )。单阴离子 LN3P2 的二芳基酰胺核衍生自双(2-氨基-4-甲基苯基)胺,其与两当量的 2-(二苯基膦酰基)苯甲醛缩合以提供具有芳基膦和亚胺供体的螯合臂。X 射线结构、磁性和光谱研究表明 N3P2 配位环境通常促进低自旋配置。在每个复合物的伏安研究中观察到了 +1.0 和 –1.5 V(vs. Fc+/Fc)之间的三个准可逆氧化还原对,对应于 MII/MIII 氧化、基于 LN3P2 的氧化、和 MII/MI 减少(按潜力从高到低的顺序)。通过 3 的化学单电子氧化生成的 3ox 的光谱和计算分析表明,氧化后形成稳定的二芳基胺基
Bimetallic Complexes Supported by a Redox-Active Ligand with Fused Pincer-Type Coordination Sites
作者:Denan Wang、Sergey V. Lindeman、Adam T. Fiedler
DOI:10.1021/acs.inorgchem.5b01380
日期:2015.9.8
structures in which each M(II) ion (M = Co, Cu, Zn) is bound in a meridional fashion by the bridging diarylamido N atom and O,N-donors of the salicyaldimine arms. The metal centers are also coordinated by a mono- or bidentate auxiliary ligand (Laux), resulting in complexes with the general form [M2(LN3O2)(Laux)2]+ (where Laux = 1-methyl-benzimidazole (1MeBI), 2,2′-bipyridine (bpy), 4,4′-dibromo-2,2′-bipyridine