2,2',2"-trimercapto-3,3',3"-tris(trimethylsilyl)triphenylphosphine | 119327-24-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,2',2"-trimercapto-3,3',3"-tris(trimethylsilyl)triphenylphosphine
• 英文别名: P(o-C6H3-3-SiMe3-2-SH)3；P(C6H3-3-Me3Si-2-SH)3；P(C6H3-3-SiMe3-2SH)3；2-Bis(2-sulfanyl-3-trimethylsilylphenyl)phosphanyl-6-trimethylsilylbenzenethiol
• CAS: 119327-24-1
• 化学式: C₂₇H₃₉PS₃Si₃
• 分子量: 575.035
• InChiKey: VWRJSGPXHSNGEK-UHFFFAOYSA-N

物化性质

• 沸点：
  566.2±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.95
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  3
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2',2"-trimercapto-3,3',3"-tris(trimethylsilyl)triphenylphosphine 在 [(C₂H₅)3O][BF₄] 作用下， 以 四氢呋喃 为溶剂， 生成 [Ni(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]2
  参考文献：
  名称：

  Mononuclear Ni(II)-Thiolate Complexes with Pendant Thiol and Dinuclear Ni(III/II)-Thiolate Complexes with Ni···Ni Interaction Regulated by the Oxidation Levels of Nickels and the Coordinated Ligands

  摘要：

  Compared to [Ni-II(SePh)(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (1a) and [Ni-II(Cl)(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (3a) with a combination of the intramolecular [Ni center dot center dot center dot H-S] and [Ni-S center dot center dot center dot H-S] interactions, complexes (Ni-II(SePh)(P(o-C6H3-3-Sime(3)-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (1b) and [Ni-II(Cl)(P (o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (3b) with intramolecular [Ni center dot center dot center dot H-S] interaction exhibit lower nu(S-H) stretching frequencies (2137 and 2235 cm(-1) for 1b and 3b vs 2250 and 2287 cm(-1) for 1a and 3a, respectively) and smaller torsion angles (27.20 for 3b vs 58.9 and 59.1 degrees for 1a and 3a, respectively). The pendant thiol interaction modes of 1a, 3a, and 3b in the solid state are controlled by the solvent pairs of crystallization. Oxygen oxidation of dinuclear [Ni-II(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](2) (4) yielded thermally stable dinuclear [Ni-III(P(o-C6H3-3-SiMe3-2S)(2)(o-C6H3-3-SiMe3-2-mu-S))](2) (5). The two paramagnetic d(7) Ni-II cores (S = 1/2) with antiferromagnetic coupling (J = -3.13 cm(-1)) rationalize the diamagnetic property of 5. The fully delocalized mixed-valence [Ni(II)-Ni(III)] complexes [Ni-2(P(o-C6H3-3-SiMe3-2-S)(3))(2)](-) (6) and [Ni-2(P(o-C6H3-3-SiMe3-2-S)(3))(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-siMe(3)-2-SCH3))] (7) were isolated upon the reduction of 5 and the methylation of 6, respectively. The electronic perturbation from the sulfur methylation of 6 triggers the stronger Ni center dot center dot center dot Ni interaction and the geometrical rearrangement from the diamond shape of the [NiS2Ni] core to the butterfly structure of [Ni(mu-S)(2)Ni] to yield 7 with Ni center dot center dot center dot Ni distances of 2.6088(1) angstrom. The distinctly different Ni center dot center dot center dot Ni distances (2.6026(7) for 5 and 2.8289(15) angstrom for 6) and the coordination number of the nickels indicate a balance of geometrical requirements for different oxidation levels of [PS3Ni-NiPS3] cores of 5 and 6.

  DOI：

  10.1021/ic700719h
• 作为产物：
  描述：

  2-trimethylsilylbenzenethiol 在 正丁基锂 、 四甲基乙二胺 、 三氯化磷 作用下， 生成 2,2',2"-trimercapto-3,3',3"-tris(trimethylsilyl)triphenylphosphine
  参考文献：
  名称：

  2-Phosphino- and 2-phosphinylbenzenethiols: new ligand types

  摘要：

  DOI：

  10.1021/ja00188a071

文献信息

• Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid–Base Chemistry of Thiol and Thiolate
  作者：Jyun-An Yan、Yu-Sen Chen、Ya-Ho Chang、Cheng-Yun Tsai、Chiao-Ling Lyu、Chun-Gang Luo、Gene-Hsiang Lee、Hua-Fen Hsu

  DOI：10.1021/acs.inorgchem.7b01040

  日期：2017.8.7

  deprotonation of unbound thiol to bound thiolate. Complex 3 is also produced from complex 2 through stepwise addition of Fe(Cp)2+/n-BuLi, or in the reverse order. The formation of 2 from 3 is achieved in the order of adding Co(Cp)2 and acid or, as with the previous complex, inversely. Notably, the reduction of complex 2 to complex 1 accompanying the protonation of bound thiolate to unbound thiol only

  非氧化钒硫中心的氧化还原性质与多种生物系统有关，例如钒固氮酶，海鞘中钒离子的还原以及阿瓦达丁的功能，而阿马瓦丁是鹅膏菌蘑菇中所含的钒（IV）天然产物。但是由于高价钒离子的亲氧特性，与氧化钒相比，对相关化学的研究和了解较少。在这里，我们提出了一类非氧化型硫氧钒钒配合物[V III（PS2″ S H）2 ] -（1）（PS2″ S H = [P（C 6 H 3 -3-Me 3 Si-2 -S）2（C6 H 3 -3-Me 3 Si-2-SH）] 2–），[V IV（PS3″）（PS2″ S H）] −（2）（PS3″ = [P（C 6 H 3 -3 -Me 3 Si-2-S）3 ] 3–），[V（PS3″）2 ] -（3），[V（PS3″）（PS2″ S H）]（4）和[V IV（ PS3 *）2 ] 2–（5a）（PS3 * = [P（C 6 H 3 -3-Ph-2-S）3 ] 3–），并通
• Trigonal-Bipyramidal Tin(IV) Complexes Containing Tetradentate Tripodal Tristhiolatophosphine Ligands:  Synthesis, Characterization, Crystal Structure, and Transmetalation Reactions
  作者：Kerry A. (Fusie) Clark、T. Adrian George

  DOI：10.1021/ic049328+

  日期：2005.1.1

  Byproducts frequently found in the synthesis of the proligands and tin complexes, and subsequent reactions, result from the oxidation of the trianionic tristhiolatophosphine ligand. The crystal structure of one of these, [OP((H)S(3))](2), shows that the molecule contains two ligands joined by a S-S bond. Within each original ligand the remaining two sulfur atoms form a S-S bond, and each phosphorus

  配体P（C（6）H（4）-2-SH）（3）（P（（H）SH）（3）），P（C（6）H（3）的锂盐的反应-3-SiMe（3）-2-SH）（3）（P（（TMS）SH）（3））和P（C（6）H（3）-5-Me-2-SH）（3 ）（P（（Me）SH）（3））与RSnCl（3）（R = Ph，Me，n-Bu），在0度的THF中，产生一系列RSn（ PS（3））。PhSn（P（H）S（3）），PhSn（P（TMS）S（3））和PhSn（P（Me）S（3））的晶体结构显示出局部C（3v）对称性引起的相当大的畸变对于Sn（PS（3））组。PhSn（P（Me）S（3））的独特之处在于一个硫原子与Ph基团的邻位H原子之间存在分子内氢键，从而形成了一个包含该S原子和相应C（6）H的平面（3）环，一个磷原子和PhSn基团。对HMQC，HMBC，2-D COSY的组合进行的（1）H，（13）C和（31）P NMR数据的分析，和（1）H
• Catalytic Reduction of Hydrazine to Ammonia by a Mononuclear Iron(II) Complex on a Tris(thiolato)phosphine Platform
  作者：Ya-Ho Chang、Pooi-Mun Chan、Yi-Fang Tsai、Gene-Hsiang Lee、Hua-Fen Hsu

  DOI：10.1021/ic402108w

  日期：2014.1.21

  To provide the mechanistic information of nitrogenase at a molecular level, much effort has been made to develop synthetic metal complexes that have enzyme-like reactivity. Herein we obtain an iron(II) complex binding with a tris(thiolato)phosphine ligand, [P(Ph)4][Fe(PS3″)(CH3CN)] [1; PS3″ = P(C6H3-3-Me3Si-2-S)33–] that catalyzes the reduction of hydrazine, an intermediate and a substrate of nitrogenase

  为了在分子水平上提供固氮酶的机械信息，已经进行了很多努力来开发具有酶样反应性的合成金属络合物。在本文中，我们获得了与三（硫代）膦配体[P（Ph）4 ] [Fe（PS3''）（CH 3 CN）] [ 1结合的铁（II）配合物。PS3''= P（C 6 H 3 -3-Me 3 Si-2-S）3 3– ]，可催化肼（一种中间体和一种固氮酶）的还原。与底物和产物结合的加合物，[N（Bu）4 ] [Fe（PS3″）（N 2 H 4）]（2）和[N（Et）4 ] [Fe（PS3″）（NH 3））]（3）分别也被合成。这项工作提供了可行性，即可以在具有富硫连接环境的单个铁位点进行生物固氮的后期阶段。
• Structural and Spectroscopic Characterization of a Monomeric Side-On Manganese(IV) Peroxo Complex
  作者：Chien-Ming Lee、Chi-He Chuo、Ching-Hui Chen、Cho-Chun Hu、Ming-Hsi Chiang、Yu-Jan Tseng、Ching-Han Hu、Gene-Hsiang Lee

  DOI：10.1002/anie.201201735

  日期：2012.5.29

  Gotcha: The binding and activation of oxygen by a manganese complex is reported. A PS3 coordination sphere built around a manganese(I) center facilitates the isolation of a monomeric manganese(IV) peroxo complex that is stable at ambient temperature (see picture). The activation of molecular oxygen is proposed via a manganese(II) intermediate with an empty site for the binding of the substrate.

  陷阱：锰配合物对氧的结合和活化有报道。围绕锰（I）中心构建的PS 3配位球有助于分离在环境温度下稳定的单体锰（IV）过氧配合物（参见图片）。分子氧的活化是通过锰（II）中间体提出的，该中间体具有用于结合底物的空位。
• Non-oxido divanadium(<scp>iv</scp>) and divanadium(<scp>v</scp>) thiolate complexes with a new type of chalcogenide bridging motif
  作者：Hong-Ming Wu、Ya-Ho Chang、Yi-Fang Tsai、Kuei-Fang Hsu、Gene-Hsiang Lee、Hua-Fen Hsu

  DOI：10.1039/c4dt03934c

  日期：——

  In our effort to study vanadium chalcogenide chemistry, we have synthesized and characterized a class of non-oxido divanadium(IV) and divanadium(V) complexes with chalcogenide and dichalcogenide as bridges. All structures consist of a similar divanadium motif, in which two metal centers are bridged by one μ-chalcogenide and one μ–η2:η2-dichalcogenide, forming a V2(μ-E)(μ–η2:η2-E2) (E = S or Se) core

  在研究钒硫属元素化物化学的过程中，我们合成并表征了一类以硫属元素化物和二硫代gen啶为桥的非氧化二钒（IV）和二钒（V）配合物。所有结构由类似的二钒基序，其中两个金属中心由一个μ-硫属化物和一种μ-η桥接的2：η 2 -dichalcogenide，形成V 2（μ-E）（μ-η 2：η 2 -E 2）（E = S或SE）核心结构。这些化合物是[V IV 2（PS3）2（μ-硒2）（μ-SE）] [PPH 4 ] 2（1），[V V 2（PS3''） 2（μ-硒2）（μ-SE）]（2），[V V 2（PS3''） 2（μ-S 2）（μ-S）] （图3a）和[V V 2（PS3）2（μ-S 2）（μ-S）]（3B）（[PS3] -3- = P（C 6 H ^ 4 -2-S）3和[PS3的′] 3− = P（C 6 H 3 -3-SiMe 3 -2-S）3）。化合物1表现出抗磁特性，表明两个d