Department of Biochemistry, Chemistry, Physics, and Engineering, Commonwealth University of Pennsylvania-Bloomsburg, 400 E. Second Street, Bloomsburg, Pennsylvania 17815, United States.
Inorg Chem. 2023 Jun 19;62(24):9618-9629. doi: 10.1021/acs.inorgchem.3c01099. Epub 2023 Jun 9.
The synthesis and structural characterization of 16 new thallium lanthanide squarate complexes and 1 new cerium squarate oxalate complex are presented. These new complexes─Tl[Ln(CO)(HO)]·CO (Ln = La-Nd) (), Tl[Ln(CO)(HO)]·8HO (Ln = Sm-Lu, Y) (), Tl[Ce(CO)(HO)]·CO (), and [Ce(CO)(CO)(HO)]·2HO ()─all contain the squarate ligand bound to the trivalent lanthanides with varying coordination modes and denticities. Of the four new groups of complexes prepared in this work, two groupings contain monovalent thallium and trivalent lanthanides, the most common oxidation states for these metals. One complex (), however, contains trivalent thallium, which is an unusual and challenging oxidation state to stabilize. The Tl cation is formed from oxidation by way of tetravalent cerium (Ce/Ce, ° = 1.72 V; Tl/Tl = 1.252 V), leading to the formation of a Tl-Ce-squarate complex. Additionally, one complex () is unique in this work in that it contains both the squarate and oxalate ligands, the latter of which was formed from squarate. Single-crystal X-ray diffraction analysis reveals that and have a 2D structure constructed from either LnO(HO) monocapped square antiprismatic (CN = 9) metal centers (for ) or LnO(HO) square antiprismatic (CN = 8) metal centers (for ), is a 1D chain structure constructed from CeO(HO) monocapped square antiprismatic (CN = 9) cerium centers, and is a 3D framework structure constructed from CeO(HO) monocapped square antiprismatic (CN = 9) cerium centers. and display rare coordination modes for the squarate ligand. Herein, the synthesis, characterization, and structural descriptions of these new complexes are presented.
本文介绍了 16 种新型铊镧系 squarate 配合物和 1 种新型铈 squarate 草酸盐配合物的合成及结构表征。这些新配合物─Tl[Ln(CO)(HO)]·CO（Ln = La-Nd）（）、Tl[Ln(CO)(HO)]·8HO（Ln = Sm-Lu、Y）（）、Tl[Ce(CO)(HO)]·CO（）和[Ce(CO)(CO)(HO)]·2HO（）─均含有与三价镧系元素配位的 squarate 配体，其配位方式和齿数有所不同。在本工作中制备的四组新配合物中，有两组包含单价铊和三价镧系元素，这是这两种金属最常见的氧化态。然而，有一种配合物（）含有三价铊，这是一种难以稳定的异常氧化态。Tl 阳离子是由四价铈（Ce/Ce，°=1.72 V；Tl/Tl=1.252 V）氧化形成的，导致形成了 Tl-Ce-squarate 配合物。此外，在本工作中，有一种配合物（）是独特的，它同时含有 squarate 和 oxalate 配体，后者是由 squarate 形成的。单晶 X 射线衍射分析表明，和具有二维结构，分别由 LnO(HO)单帽四方反棱柱（CN = 9）金属中心（对于）或 LnO(HO)四方反棱柱（CN = 8）金属中心（对于）构建，是由 CeO(HO)单帽四方反棱柱（CN = 9）铈中心构建的一维链结构，是由 CeO(HO)单帽四方反棱柱（CN = 9）铈中心构建的三维框架结构。和显示了 squarate 配体的罕见配位模式。本文介绍了这些新配合物的合成、表征和结构描述。
