Redox Communication between Two Diarylamido/Bis(phosphine) (PNP)M Moieties Bridged by Ynediyl Linkers (M = Ni, Pd, Pt).
Redox Communication between Two Diarylamido/Bis(phosphine) (PNP)M Moieties Bridged by Ynediyl Linkers (M = Ni, Pd, Pt).
复制标题
两个二芳基酰胺基/双（膦）（PNP）M 部分之间通过 Ynediyl 连接体（M = Ni、Pd、Pt）桥接的氧化还原通讯。
作者：
Cheng;Xin Yang;Xiaozhou Ji;Chen‐Hao Wang;Qingheng Lai;N. Bhuvanesh;O. Ozerov
合成了一系列双核同、杂环配合物（PNP）M-[linker]-M（PNP）（M = Ni，Pd，Pt; PNP =二芳酰胺/双膦钳形配体; -[linker]- = -C≡C-，-C≡CC≡C-，-C≡ CC 6 H 4C ≡C-）。每个（PNP）M网站可以被一个电子氧化，这项工作报告的调查的混合价行为的两个氧化还原位点之间的通信和离域的程度在单氧化阳离子。使用循环伏安法，UV-vis-NIR和EPR光谱，X射线晶体学和DFT计算的化合物进行了评估。具有最长检测接头的络合物，（PNP）Ni-C CC 6 H4 C C-Ni（PNP）（9 Ni），在氧化还原位点之间没有表现出可辨别的通信。同双金属配合物（PNP）M-C-C-CC-C-M（PNP）（6 M）与-C-C-C-接头类似物（PNP）M-C-C-M（PNP）（3 M）相比显示出较低程度的通讯。在这两个子集中的每一个内，通信和离域的相对程度被确定为Pd < Ni <Pt。在Robin-Day标度上，化合物6 M可以被分配为I类（M = Pd）和II类（M = Ni、Pt）。配合物3 Pd也福尔斯II类，而3 Ni和3 Pt可以被视为边缘II/III类情况。这是可能的，在Ni系统中的通信具有的优势，较小的尺寸的Ni，导致在更大的物理接近的氧化还原位点，而5d金属Pt具有最大的能力，轨道相互作用的-C C-连接。
A series of binuclear homo- and heterobimetallic complexes of the general type (PNP)M-[linker]-M(PNP) have been prepared (M = Ni, Pd, Pt; PNP = a diarylamido/bis(phosphine) pincer ligand; -[linker]- = -C≡C-, -C≡CC≡C-, -C≡CC6H4C≡C-). Each (PNP)M site can be oxidized by one electron, and this work reports the investigation of the mixed-valence behavior in terms of the communication between the two redox sites and the degree of the delocalization in the monooxidized cation. The compounds were evaluated using cyclic voltammetry, UV-vis-NIR and EPR spectroscopy, X-ray crystallography, and DFT calculations. The complex with the longest examined linker, (PNP)Ni-C≡CC6H4C≡C-Ni(PNP) (9Ni), exhibited no discernible communication between the redox sites. The homobimetallic complexes (PNP)M-C≡CC≡C-M(PNP) (6M) displayed a lower degree of communication in comparison to the -C≡C- linker analogues (PNP)M-C≡C-M(PNP) (3M). Within each of these two subsets, the relative degree of communication and delocalization was determined to be Pd < Ni ≤ Pt. On the Robin-Day scale, compounds 6M can be assigned class I for M = Pd and class II for M = Ni, Pt. Complex 3Pd also falls into class II, while 3Ni and 3Pt may be viewed as borderline class II/III cases. It is likely that the communication in the Ni systems has the advantage of the smaller size of Ni, resulting in a greater physical proximity of the redox sites, while the 5d metal Pt possesses the greatest ability for orbital interaction with the -C≡C- linker.
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