Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
Inorg Chem. 2020 Jul 6;59(13):9279-9286. doi: 10.1021/acs.inorgchem.0c01163. Epub 2020 Jun 18.
We outline the generality and requirements for cooperative NH 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-NH stabilization. While the Lewis acids are required to bind NH, 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.
我们概述了一系列含吡啶（二吡唑）配体的第一过渡金属配合物中 NH 捕获、N-N 键断裂和酰胺稳定的通用性和要求。该配体含有一对灵活连接的三烷基硼烷路易斯酸，可实现联氨捕获和 M-NH 稳定。路易斯酸虽然需要结合 NH，但金属的身份决定了 N-N 键是否可以断裂。研究了 M(II)双（酰胺基硼烷）系列配合物的氧化还原性质，发现配体基事件占主导地位；氧化导致瞬态形成氨自由基，而还原发生在氧化还原活性吡啶（二吡唑）配体上。
