The [MoFe<sub>3</sub>S<sub>4</sub>]<sup>2+</sup> Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the <i>S</i> = 2 Ground State
作者:Bin Xi、R. H. Holm
DOI:10.1021/ic200641k
日期:2011.7.4
This work is the first comprehensive study of the [MoFe3S4]2+ state, one conspicuous feature of which is its ability to bind hard and soft σ-donors and strong to weak π-acid ligands. (Tp = tris(pyrazolyl)hydroborate(1-))
簇 [(Tp)MoFe 3 S 4 (PEt 3 ) 3 ] 1+包含立方烷型 [MoFe 3 (μ 3 -S) 4 ] 2+还原核在铁位点发生容易的配体取代反应,导致广泛的单取代和双取代物种 [(Tp)MoFe 3 S 4 (PEt 3 ) 3– n L n ] 1– n,其中 L = 卤化物、N 3 –、PhS –、PhSe –、R 3 SiO –, 和 R 3 SiS –并且n = 1 和 2。报告了该集合的 10 个成员的结构。对于两个有代表性的集群,居里行为在 2-20 K 表示自旋五重奏基态。零场穆斯堡尔光谱由强度比为 2:1 的两个双峰组成。57 Fe 异构体位移与平均氧化态 Fe 3 2.33+一致,该平均氧化态来自混合价氧化态描述 [Mo 3+ Fe 3+ Fe 2+ 2 ] 的电子离域。[(Tp)MoFe 3 S 4 (PEt 3 ) 2 Cl] 与 (Me 3 Si)
Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes
作者:Daniel J. Meininger、Max Chee-Garza、Hadi D. Arman、Zachary J. Tonzetich
DOI:10.1021/acs.inorgchem.5b02822
日期:2016.3.7
Gallium(III) tetraphenylporphyrinates (TPP) containing anionic sulfur ligands have been prepared and characterized in the solid state and solution. The complexes serve as structural models for iron(III) heme sites containing sulfur coordination that otherwise prove challenging to synthesize due to the propensity for reduction to iron(II). The compounds prepared include the first well-characterized
已制备了含有阴离子硫配体的四苯基卟啉镓(III)(TPP),并在固态和溶液中进行了表征。该络合物用作包含硫配位的铁(III)血红素位点的结构模型,否则由于还原成铁(II)的倾向而证明合成具有挑战性。所制备的化合物包括第一个很好表征的三价金属卟啉酸盐,其中包含末端氢硫化物配体[Ga(SH)(TPP)]以及[Ga(SEt)(TPP)],[Ga(SPh)(TPP) )]和[Ga(SSi i Pr 3)(TPP)]。这些化合物对还原的稳定性允许对其固态结构和电化学进行研究。讨论了与铁(III)类似物有关的配合物的结构特征和反应化学。
Thiols, unsymmetrical sulfides and thioacetals from the new reagent: Triisopropylsilanethiol
作者:Edgar I. Miranda、Michael J. Díaz、Izander Rosado、John A. Soderquist
DOI:10.1016/s0040-4039(00)76869-9
日期:1994.5
Triisopropylsilanethiol (HSTIPS, 1), easily prepared in 98% yield from H2S and TIPSCl, is efficiently alkylated in a selective manner with 1° and 2° alkyl halides or tosylates through its potassium thiolate (2c) to provide RSTIPS (3) in excellent yields. Compound 3 provides a convenient source of alkanethiols (4), unsymmetrical dialkyl sulfides (5) and thioacetals (6).
Preparation of ruthenium silanethiolato complexes and their reactions with sulfur dioxide; possible models for the activation of SO2 in the homogeneously catalyzed Claus reaction
作者:Istvan Kovacs、Celine Pearson、Alan Shaver
DOI:10.1016/s0022-328x(99)00678-6
日期:2000.2
unstable CpRu(PPh3)(SO2)SSiiPr3 (6f). However, complexes 6b–e inserted one equivalent of SO2 solely at their SSiiPr3 function to give the unstable O-silyl thiosulfito complexes CpRu(PPh3)(L)SS(O)OSiiPr3 (L=CO (8b), PMe3 (8c), P(OMe)3 (8d)) as well as CpRu(dppe)SS(O)OSiiPr3 (8e). The SH bonds of CpRu(PPh3)2SH (7a) and CpRu(dppe)SH (7b) added to PhNSO to give CpRu(PPh3)2SS(O)NHPh (9a) and CpRu(dppe)SS(O)NHPh
通过使[CpRu(PPh 3)2(丙酮)] BF 4与NaSSi i Pr 3反应制备CpRu(PPh 3)2 SSi i Pr 3(6a)。配合物6a对取代不稳定,容易得到混合配体衍生物CpRu(PPh 3)(L)SSi i Pr 3,其中L = CO(6b),PMe 3(6c),P(OMe)3(6d),在用相应的配体处理后。CpRu(dppe)SSi i Pr 3(图6e)从复杂获得图6a和DPPE经由CPRU的中间形成(PPH 3)(η 1 -dppe)SSI我镨3。用一当量的SO 2处理配合物6a主要产生不稳定的CpRu(PPh 3)(SO 2)SSi i Pr 3(6f)。然而,复合物6B - ë插入一个当量的SO 2仅在它们的SSi我镨3函数,得到不稳定ø -甲硅烷基络合物thiosulfito CPRU(PPH3)(L)SS(O)OSi i Pr 3(L = CO(8b),PMe
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