Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization
Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization
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DOI：
10.1021/acs.inorgchem.0c01163
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发表时间：
2020-07-06
影响因子：
4.6
通讯作者：
Szymczak, Nathaniel K.
中科院分区：
文献类型：
--
作者：
Kiernicki, John J.;Zeller, Matthias;Szymczak, Nathaniel K.
我们概述了一系列含吡啶(联吡唑)配体的第一排过渡金属配合物对N2H4的协同捕获、N-N键断裂和氨基稳定的共性和要求。该配体含有一对灵活连接的三烷基硼路易斯酸，能够捕获联氨和稳定M-NH2。虽然路易斯酸是结合N2H4所必需的，但金属的特性决定了N-N键是否会发生断裂。研究了M(II)双(酰胺基硼烷)系列配合物的氧化还原性质，发现以配体为基础的反应占主导地位；氧化生成瞬时生成的氨基自由基，而还原发生在氧化还原活性的吡啶(联吡唑)配体上。
We outline the generality and requirements for cooperative N2H4 capture, N-N bond scission, and amido stabilization across a series of first-row transition metal complexes bearing a pyridine(dipyrazole) ligand. This ligand contains a pair of flexibly tethered trialkylborane Lewis acids that enable hydrazine capture and M-NH2 stabilization. While the Lewis acids are required to bind N2H4, the identity of the metal dictates whether N-N bond scission can occur. The redox properties of the M(II) bis(amidoborane) series of complexes were investigated and reveal that ligand-based events prevail; oxidation results in the generation of a transiently formed aminyl radical, while reduction occurs at the redox-active pyridine(dipyrazole) ligand.