Selenium as a structural surrogate of sulfur: template-assisted assembly of five types of tungsten-iron-sulfur/selenium clusters and the structural fate of chalcogenide reactants.
Selenium as a structural surrogate of sulfur: template-assisted assembly of five types of tungsten-iron-sulfur/selenium clusters and the structural fate of chalcogenide reactants.
复制标题
DOI：
10.1021/ja3010539
复制
发表时间：
2012-04-11
影响因子：
15
通讯作者：
Holm, R. H.
中科院分区：
文献类型：
--
作者：
Zheng, Bo;Chen, Xu-Dong;Zheng, Shao-Liang;Holm, R. H.
基于模板辅助组装的概念，设计合成了五种类型的钨-铁-硫/硒簇合物：不完全立方烷、单立方烷、边桥双立方烷（EBDC）、PN型簇合物和双立方簇合物。模板反应物是六配位[（Tp*）WVIS 3]1-，其在组装系统中将Fe II、III和硫化物/硒化物组织成立方体[（Tp*）WFe 2S 3]或立方烷[（Tp*）WFe 3S 3Q]单元。通过适当的末端铁连接，这些单位能够独立存在或转化为更高核数的物种。硒化物被用作硫化物的替代品在集群组装，以确定由外部硫属元素亲核试剂或内部硫属元素原子在产品集群中所占据的位置，通过X射线结构。通过形成[WFe_3S_3Se]~（2+），3 ~+立方烷核来证明硒化物的特异性掺入。立方烷的还原二聚导致EBDC核心[W2 Fe 6S 6Se 2]2+含有μ4-Se位点。这些物质与HSe-反应得到PN型核[W2 Fe 6S 6Se 3]1+，其中硒化物占据μ6-Se和μ2-Se位点。[（Tp*）WS 3]1−、FeCl 2和Na 2Se反应生成具有μ2-Se和μ4-Se桥的双立方[W2 Fe 4S 6Se 3]2+，0核。在类似的仅含硫化物的组装系统中，外部和内部硫化物反应物在簇产物中占据相应的位置是非常可能的。结果进一步证明了模板辅助簇合成的可行性，因为还原的（Tp*）WS 3单元存在于所有簇中。结构，零场穆斯堡尔谱数据，和氧化还原电位的所有集群类型。(Tp* =三（吡唑基）硼氢化物（1-））
Syntheses of five types of tungsten-iron-sulfur/selenium clusters–incomplete cubanes, single cubanes, edge-bridged double cubanes (EBDCs), PN-type clusters, and double-cuboidal clusters–have been devised based on the concept of template-assisted assembly. The template reactant is six-coordinate [(Tp*)WVIS3]1−, which in the assembly systems organizes FeII,III and sulfide/selenide into cuboidal [(Tp*)WFe2S3] or cubane [(Tp*)WFe3S3Q] units. With appropriate terminal iron ligation, these units are capable of independent existence or may be transformed into higher nuclearity species. Selenide is used as a surrogate for sulfide in cluster assembly in order to determine by X-ray structures the position occupied by an external chalcogenide nucleophile or an internal chalcogenide atom in product clusters. Specific incorporation of selenide is demonstrated by formation of [WFe3S3Se]2+,3+ cubane cores. Reductive dimerization of the cubane leads to the EBDC core [W2Fe6S6Se2]2+ containing μ4-Se sites. Reaction of these species with HSe− affords the PN-type cores [W2Fe6S6Se3]1+ in which selenide occupies μ6-Se and μ2-Se sites. Reaction of [(Tp*)WS3]1−, FeCl2, and Na2Se results in the double cuboidal [W2Fe4S6Se3]2+,0 core with μ2-Se and μ4-Se bridges. It is highly probable that in analogous sulfide-only assembly systems, external and internal sulfide reactants occupy corresponding positions in cluster products. The results further demonstrate the viability of template-assisted cluster synthesis inasmuch as the reduced (Tp*)WS3 unit is present in all clusters. Structures, zero-field Mössbauer data, and redox potentials are presented for all cluster types. (Tp* = tris(pyrazolyl)hydroborate(1−))
登录
查看更多内容
影响因子：
2.3
作者：
Komuro, Takashi;Kawaguchi, Hiroyuki;Tatsumi, Kazuyuki
通讯作者：
Tatsumi, Kazuyuki
影响因子：
2.9
作者：
Kung, Yan;Doukov, Tzanko I.;Seravalli, Javier;Ragsdale, Stephen W.;Drennan, Catherine L.
通讯作者：
Drennan, Catherine L.
影响因子：
4.6
作者：
Arikawa, Y;Kawaguchi, H;Tatsumi, K
通讯作者：
Tatsumi, K
影响因子：
56.9
作者：
Einsle, O;Tezcan, FA;Rees, DC
通讯作者：
Rees, DC
影响因子：
56.9
作者：
Jeoung, Jae-Hun;Dobbek, Holger
通讯作者：
Dobbek, Holger