Melman Jonathan H., Emge Thomas J., Brennan J. G.
Department of Chemistry, Rutgers, the State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854-8087.
Inorg Chem. 1999 May 3;38(9):2117-2122. doi: 10.1021/ic981122j.
Octanuclear (THF)(8)Ln(8)S(6)(SPh)(12).xTHF clusters (Ln = lanthanide ion) can be isolated from the reactions of Ln(SPh)(3) with elemental S. Complexes have been isolated successfully for Ln = Ce (1), Pr (2), Nd (3), Sm (5), Gd (6), Tb (7), Dy (8), Ho (9), and Er (10). Only the Ce and Sm compounds are intensely colored, due to a relatively low energy f( )(1)-to-d(1) promotion for 1 and a S(2)(-) to Sm charge transfer absorption for 5. The complexes are all thermally unstable with respect to loss of THF at room temperature. The reaction of Sm(SPh)(3) with S in a THF/DME mixture gives thermally unstable (THF)(8)Ln(8)S(6)(SPh)(12).6DME (4). The analogous pyridine (py) complexes (py)(8)Ln(8)S(6)(SPh)(12).xpy (Ln = Nd (11), Sm (12), Er (13)) were also found to desolvate at room temperature. All compounds have been characterized by conventional methods and by low-temperature single-crystal X-ray diffraction. Complete structural analyses have been obtained for compounds 4, 7, 12, and 13, and the structures of the rest were confirmed by unit cell determinations. In each case, the same basic octanuclear framework, with a cube of metal atoms connected by S(2)(-) ligands capping the faces of the cube, and SPh ligands spanning the edges of the cube, is observed. Differences in the structures originate either in the relative orientation of the Ph moieties or in the number and orientations of the lattice solvent molecules. The Ce cluster is isostructural with (THF)(8)Sm(8)Se(6)(SePh)(12), compounds 2 and 3 are isostructural with the previously reported structure of 6, clusters 5 and 8-10 are isostructural with 7, and cluster 11 is isostructural with 12.
八核(THF)(8)Ln(8)S(6)(SPh)(12).xTHF簇合物（Ln = 镧系离子）可通过Ln(SPh)(3)与元素硫的反应分离得到。对于Ln = Ce (1)、Pr (2)、Nd (3)、Sm (5)、Gd (6)、Tb (7)、Dy (8)、Ho (9)和Er (10)，已成功分离出配合物。只有Ce和Sm化合物有强烈颜色，这是由于1中f( )(1)到d(1)的跃迁能量相对较低，以及5中S(2)(-)到Sm的电荷转移吸收。这些配合物在室温下对于THF的损失都是热不稳定的。Sm(SPh)(3)与硫在THF/DME混合物中的反应生成热不稳定的(THF)(8)Ln(8)S(6)(SPh)(12).6DME (4)。还发现类似的吡啶（py）配合物（py)(8)Ln(8)S(6)(SPh)( – 12).xpy（Ln = Nd (11)、Sm (12)、Er (13)）在室温下会去溶剂化。所有化合物均通过常规方法和低温单晶X射线衍射进行了表征。已获得化合物4、7、12和13的完整结构分析，其余化合物的结构通过晶胞测定得到确认。在每种情况下，都观察到相同的基本八核框架，即由S(2)(-)配体连接的金属原子立方体覆盖立方体的面，SPh配体跨越立方体的边。结构差异要么源于Ph基团的相对取向，要么源于晶格溶剂分子的数量和取向。Ce簇合物与(THF)(8)Sm(8)Se(6)(SePh)(12)同构，化合物2和3与先前报道的6的结构同构，簇合物5和8 - 10与7同构，簇合物11与12同构。
