Wong Janice L, Higgins Robert F, Bhowmick Indrani, Cao David Xi, Szigethy Géza, Ziller Joseph W, Shores Matthew P, Heyduk Alan F
Department of Chemistry , University of California , Irvine , California 92697 , USA . Email:
Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , USA . Email:
Chem Sci. 2016 Feb 1;7(2):1594-1599. doi: 10.1039/c5sc03006d. Epub 2015 Dec 8.
A new bimetallic platform comprising a six-coordinate Fe(ONO) unit bound to an (ONO)M (M = Fe, Zn) has been discovered ((ONO)H = bis(3,5-di--butyl-2-phenol)amine). Reaction of Fe(ONO) with either (ONO)Fe(py) or with (ONO)FeCl under reducing conditions led to the formation of the bimetallic complex Fe(ONO), which includes unique five- and six-coordinate iron centers. Similarly, the reaction of Fe(ONO) with the new synthon (ONO˙)Zn(py) led to the formation of the heterobimetallic complex FeZn(ONO), with a six-coordinate iron center and a five-coordinate zinc center. Both bimetallic complexes were characterized by single-crystal X-ray diffraction studies, solid-state magnetic measurements, and multiple spectroscopic techniques. The magnetic data for FeZn(ONO) are consistent with a ground state = 3/2 spin system, generated from a high-spin iron(ii) center that is antiferromagnetically coupled to a single (ONO˙) radical ligand. In the case of Fe(ONO), the magnetic data revealed a ground state = 7/2 spin system arising from the interactions of one high-spin iron(ii) center, one high-spin iron(iii) center, and two (ONO˙) radical ligands.
一种新的双金属平台被发现，它由一个与(ONO)M（M = Fe、Zn）相连的六配位Fe(ONO)单元组成（(ONO)H = 双(3,5-二叔丁基-2-苯酚)胺）。在还原条件下，Fe(ONO)与(ONO)Fe(py)或(ONO)FeCl反应生成双金属配合物Fe(ONO)，其中包含独特的五配位和六配位铁中心。同样，Fe(ONO)与新的合成子(ONO˙)Zn(py)反应生成异双金属配合物FeZn(ONO)，其具有一个六配位铁中心和一个五配位锌中心。这两种双金属配合物均通过单晶X射线衍射研究、固态磁性测量和多种光谱技术进行了表征。FeZn(ONO)的磁性数据与基态S = 3/2自旋体系一致，该体系由一个高自旋铁(II)中心与一个单(ONO˙)自由基配体反铁磁耦合产生。对于Fe(ONO)，磁性数据显示基态S = 7/2自旋体系源于一个高自旋铁(II)中心、一个高自旋铁(III)中心和两个(ONO˙)自由基配体的相互作用。
