Heterobimetallic {PtMn} and {PtFe} lantern complexes with exceptionally long metallophilic contacts
Heterobimetallic {PtMn} and {PtFe} lantern complexes with exceptionally long metallophilic contacts
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DOI：
10.1016/j.ica.2019.04.054
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发表时间：
2019-07-01
影响因子：
2.8
通讯作者：
Doerrer, Linda H.
中科院分区：
文献类型：
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作者：
Beach, Stephanie A.;Zuckerman, Linda A.;Doerrer, Linda H.
合成了一系列新的杂双金属灯配合物[PtM(SAc)(4)(pySMe)] (M = Mn (1), Fe (2), Co (3), Ni (4), Zn(5))，以及先前报道的系列的补充，[PtM(SAc)(4)(pyNH(2))] = Mn (6), Fe(7))，并进行了彻底的表征。值得注意的是，化合物1和6是第一个晶体学表征的中性Pt-Mn含灯笼配合物。化合物2和7是具有吡啶基轴向配体的含Pt-Fe灯笼配合物的第一个例子。这些新合成的配合物通过单晶x射线衍射和UV-vis (1-7)， H-1和C-13 NMR(5)，溶液磁化率（1-4和6-7）进行了表征，并与我们之前报道的灯笼家族进行了比较。化合物2-4是同形的，含有两种晶体独立的二聚体，具有相同的交错构象。一种二聚体具有典型的Pt中心点中心点中心点Pt亲金属相互作用，范围为3.2198(6)至3.2913(6)埃，而另一种二聚体具有更长的接触范围为3.3212(6)至3.4533(6)埃。这些后一种接触表明，在任何系统中迄今为止报道的最长的亲金相互作用。固态变温磁化率研究表明，在二聚体2、3和4的两个灯笼配合物中，三维金属中心之间存在反铁磁耦合。
A new series of heterobimetallic lantern complexes, [PtM(SAc)(4)(pySMe)] (M = Mn (1), Fe (2), Co (3), Ni (4), Zn (5)), as well as additions to the previously reported series, [PtM(SAc)(4)(pyNH(2))] = Mn (6), Fe (7)), have been synthesized and thoroughly characterized. Notably, compounds 1 and 6 are the first crystallographically characterized, neutral Pt-Mn containing lantern complexes. Compounds 2 and 7 are the first examples of Pt-Fe containing lantern complexes with a pyridine based axial ligand. These newly synthesized complexes have been characterized by single-crystal X-ray diffraction and UV-vis (1-7), H-1 and C-13 NMR spectroscopies (5), and solution magnetic susceptibility (1-4 and 6-7) and analyzed in comparison to our previously reported lantern families. Compounds 2-4 are isomorphous and contain two crystallographically independent dimers with the same staggered conformations. One dimer has a typical Pt center dot center dot center dot Pt metallophilic interaction ranging from 3.2198(6) to 3.2913(6) angstrom while the other has a much longer contact ranging from 3.3212(6) to 3.4533(6) angstrom. These latter contacts suggest metallophilic interactions that are the longest reported to date in any system. Solid state variable-temperature magnetic susceptibility studies suggest antiferromagnetic coupling between the 3d metal centers in the two lantern complexes of the dimeric forms of 2,3, and 4.