Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan, Republic of China.
Inorg Chem. 2011 Aug 15;50(16):7735-48. doi: 10.1021/ic200885h. Epub 2011 Jul 20.
When trigonal-bipyramidal clusters, [PPN][E(2)Mn(3)(CO)(9)] (E = S, Se), were treated with Cr(CO)(6) and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)(5)-incorporated HE(2)Mn(3)-complexes PPN[HE(2)Mn(3)Cr(CO)(14)] (E = S, PPN[1a]; Se, PPN[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E(2)Mn(3) square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)(5) group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA(+) salts for E(2)Mn(3)(CO)(9) were mixed with Cr(CO)(6) in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)(3)-incorporated E(2)Mn(3)Cr octahedral clusters TMBA[E(2)Mn(3)Cr(CO)(12)] (E = S, TMBA[2a]; Se, TMBA[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E(2)Mn(3)Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn(3)Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)(5)-incorporated HE(2)Mn(3)-clusters HE(2)Mn(3)Cr(2)(CO)(19) (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)(6) heated in refluxing CH(2)Cl(2). Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)(5) group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.
当三角双锥簇[PPN][E(2)Mn(3)(CO)(9)]（E=S，Se）与 Cr(CO)(6)和 PPNCl 以摩尔比 1:1:2 或 1:2:2 在 4 M KOH/MeCN/MeOH 溶液中处理时，分别形成了单-Cr(CO)(5)-掺入的 HE(2)Mn(3)-配合物PPN[HE(2)Mn(3)Cr(CO)(14)]（E=S，PPN[1a]；Se，PPN[1b]）。X 射线晶体学分析表明，1a 和 1b 是同构的，每个都显示出一个 E(2)Mn(3)正方形金字塔核，其中两个基底 E 原子中的一个与一个 Cr(CO)(5)基团和一个由一个氢原子桥接的 Mn-Mn 键外部配位。然而，当 TMBA(+)盐与E(2)Mn(3)(CO)(9)以摩尔比 1:1 在 4 M KOH/MeOH 溶液中混合并在 60°C 回流时，分别得到单-Cr(CO)(3)-掺入的 E(2)Mn(3)Cr 八面体簇TMBA[E(2)Mn(3)Cr(CO)(12)]（E=S，TMBA[2a]；Se，TMBA[2b]）。簇 2a 和 2b 是同构的，每个都由一个八面体 E(2)Mn(3)Cr 核组成，其中 Mn(3)Cr 平面的每个 Mn-Mn 或 Mn-Cr 键都由一个羰基配体半桥接。簇 1a 和 1b（具有[TMBA]盐）在 60°C 下用 KOH/MeOH 处理时，通过金属核闭合形成八面体簇 2a 和 2b。此外，发现 1a 和 1b 在加入 1 或 2 当量回流的 CH(2)Cl(2)中的 Cr(CO)(6)时，通过进一步与另一个裸露的 E 原子（E=S，3a；Se，3b）外部配位，形成双-Cr(CO)(5)-掺入的 HE(2)Mn(3)-簇HE(2)Mn(3)Cr(2)(CO)(19)（E=S，3a；Se，3b）。簇 3a 和 3b 在结构上与簇 1a 和 1b 相关，但另一个裸露的 E 原子（E=S，3a；Se，3b）进一步与一个 Cr(CO)(5)基团外部配位。在密度泛函理论的 BP86 水平上借助分子计算，从硫族元素、引入的铬羰基基团和金属骨架的角度，系统地讨论了混合锰-铬羰基硫化物和硒化物的性质、簇转化和电化学性质。
