Stabilization of 3:1 Site-Differentiated Cubane-Type Clusters in the [Fe<sub>4</sub>S<sub>4</sub>]<sup>1+</sup> Core Oxidation State by Tertiary Phosphine Ligation: Synthesis, Core Structural Diversity, and <i>S</i> = 1/2 Ground States
作者:Liang Deng、Amit Majumdar、Wayne Lo、R. H. Holm
DOI:10.1021/ic101702b
日期:2010.12.6
site-differentiated cubane-type clusters [Fe4S4(PPri3)3L] (L = Cl−, Br−, I−, RO−, RS−, RSe−) has been prepared in 40−80% yield by two methods: ligand substitution of [Fe4S4(PPri3)4]1+ in tetrahydrofuran (THF)/acetonitrile by reaction with monoanions, and reductive cleavage of ligand substrates (RSSR, RSeSeR, I2) by the all-ferrous clusters [Fe8S8(PPri3)6]/[Fe16S16(PPri3)8] in THF. These neutral clusters are stable and
广泛系列的 3:1 位点分化的立方烷型簇 [Fe 4 S 4 (PPr i 3 ) 3 L] (L = Cl - , Br - , I - , RO - , RS - , RSe - )通过两种方法以 40-80% 的产率制备:[Fe 4 S 4 (PPr i 3 ) 4 ] 1+在四氢呋喃 (THF)/乙腈中通过与单阴离子反应的配体取代,以及配体底物的还原裂解(RSSR、RSeSeR , I 2 ) 由全铁簇 [Fe 8 S8 (PPr i 3 ) 6 ]/[Fe 16 S 16 (PPr i 3 ) 8 ] 在 THF 中。这些中性簇是稳定的,不会发生涉及苯和 THF 溶液中带电物质的配体再分布反应。X 射线结构研究证实了立方烷立体化学,但 [Fe 4 S 4 ] 1+ 存在大量和可变的畸变核心来自理想化的立方核心几何形状。根据 Fe-S 键长,发现 7 个簇具有压缩的四方扭曲(4 个短键和