Influence of Multisite Metal–Ligand Cooperativity on the Redox Activity of Noninnocent N 2 S 2 Ligands
Influence of Multisite Metal–Ligand Cooperativity on the Redox Activity of Noninnocent N 2 S 2 Ligands
复制标题
多位点金属配体协同性对非无害 N 2 S 2 配体氧化还原活性的影响
DOI：
10.1021/acs.inorgchem.0c01353
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发表时间：
2020
影响因子：
4.6
通讯作者：
Daly, Scott R.
中科院分区：
文献类型：
--
作者：
Spielvogel, Kyle D.;Luna, Javier A.;Loria, Sydney M.;Weisburn, Leah P.;Stumme, Nathan C.;Ringenberg, Mark R.;Durgaprasad, Gummadi;Keith, Jason M.;Shaw, Scott K.;Daly, Scott R.
金属-配体协同效应（MLC）依赖于化学反应性配体来帮助金属与小分子结合和活化，并且它促进了前所未有的金属络合物催化的例子。尽管越来越多的兴趣结合配体为中心的化学和氧化还原反应的化学转化，有很少的研究表明，如何在MLC中的化学参与氧化还原活性配体影响其电化学性能时，绑定到金属。在这里，我们报告的模型钌配合物的氧化还原活性的逐步变化为零，一个，和两个BH 3分子进行MLC绑定与三芳基noninnocent N2 S2配体衍生fromo-苯二胺（L1）。一系列类似的钌配合物与二芳基N_2S_2配体与乙烯取代的苯（L_2）也被描述，以评估邻苯二胺亚基对氧化还原活性和MLC的影响。循环伏安法（CV）的研究和密度泛函理论（DFT）计算表明，MLC衰减配体为中心的氧化还原活性在这两个系列的配合物，但电子转移仍然实现时，只有一个的两个氧化还原活性位点上的配体是化学接合。结果表明，如何纳入一个以上的多功能反应位点可能是一个有效的策略，用于维持氧化还原noninnocent配体，也是化学反应性和MLC主管。
Metal–ligand cooperativity (MLC) relies on chemically reactive ligands to assist metals with small-molecule binding and activation, and it has facilitated unprecedented examples of catalysis with metal complexes. Despite growing interest in combining ligand-centered chemical and redox reactions for chemical transformations, there are few studies demonstrating how chemically engaging redox active ligands in MLC affects their electrochemical properties when bound to metals. Here we report stepwise changes in the redox activity of model Ru complexes as zero, one, and two BH3molecules undergo MLC binding with a triaryl noninnocent N2S2ligand derived fromo-phenylenediamine (L1). A similar series of Ru complexes with a diaryl N2S2ligand with ethylene substituted in place of phenylene (L2) is also described to evaluate the influence of theo-phenylenediamine subunit on redox activity and MLC. Cyclic voltammetry (CV) studies and density functional theory (DFT) calculations show that MLC attenuates ligand-centered redox activity in both series of complexes, but electron transfer is still achieved when only one of the two redox-active sites on the ligands is chemically engaged. The results demonstrate how incorporating more than one multifunctional reactive site could be an effective strategy for maintaining redox noninnocence in ligands that are also chemically reactive and competent for MLC.