2-(diisopropylphosphanyl)benzenethiol | 444069-41-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: 2-(diisopropylphosphanyl)benzenethiol
• 英文别名: 2-(diisopropylphosphaneyl)benzenethiol；pr(i)PSH；2-Di(propan-2-yl)phosphanylbenzenethiol
• CAS: 444069-41-4
• 化学式: C₁₂H₁₉PS
• 分子量: 226.323
• InChiKey: XPUJOOQVRCGSSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(diisopropylphosphanyl)benzenethiol 、 lead(II) chloride 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 15.0h， 以59%的产率得到Pb{(SC₆H₄-2-PⁱPr₂)-κ²-S,P}₂
  参考文献：
  名称：

  Metal Complexes (M = Zn, Sn, and Pb) of 2-Phosphinobenzenethiolates: Insights into Ligand Folding and Hemilability

  摘要：

  The divalent metal complexes M-II{(SC6H4-2-PR2)-kappa S-2,P}(2) (3-7, and 9-11) (M= Zn, Sn, or Pb; R = Pr-i, Bu-t, or. Ph); the Sn(W) complexes :Sn{(SC6H4-2-PR2)-kappa(2)-S,P}Ph2Cl (12 and 13) (R = Pr-i and Bu-t), and the ionic Sn(IV) complexes [Sn{(SC6H4-2-PR2)-kappa(2)-S,P}Ph-2[BPh4] (14 and 15) (R = Pr-i and Bu-t) have been prepared and characterized by multinuclear NMR spectroscopy and single. crystal X.-ray diffraction when suitable crystals were afforded The Sn(II) and Pb(II) complexes with R = Ph, Pr-i, or Bu-t (5, 6, 9, and 10) demonstrated ligand "folding" hinging on the P,S vector-a behavior driven by the repulsions of the metal/phosphorus and:metal/sulfur lone Pairs and increased M-S sigma bonding strength. This phenomenon Was examined by density functional theory (DFT) calculations for the compounds in both folded and unfolded states. The Sn(IV) compound 13 (R = Bu-t) crystallized with the phosphine in an axial position of the pseudotrigonal bipyramidal complex and also exhibited hemilability in the Sn P dative bond, while compound 12 (R = Pr-i), interestingly, crystallized with phosphine in an equatorial position and did not show hemilability. Finally, the crystal structure of 15 (R = Bu-t) revealed the presence of an uncommon, 4-coordinate, stable Sn(IV) cation.

  DOI：

  10.1021/ic400990n
• 作为产物：
  描述：

  氯二异丙基膦 、 苯硫酚 在 正丁基锂 、 四甲基乙二胺 、 盐酸 作用下， 以 环己烷 、 四氢呋喃 、 水 为溶剂， 反应 0.5h， 生成 2-(diisopropylphosphanyl)benzenethiol
  参考文献：
  名称：

  用氧化还原非无害钴 2-膦基苯硫醇络合物电催化合成气生成

  摘要：

  合成了由 2-(二异丙基膦酰基) 苯硫醇配体负载的钴配合物，并对其电子结构和反应活性进行了研究。X 射线衍射研究表明，钴中心周围呈方形平面几何形状，膦配体呈反式排列。密度泛函理论计算和电子光谱测量表明混合金属-配体轨道特征，类似于先前研究的二硫烯和二硒烯系统。在 1 个大气压的 CO 2和布朗斯台德酸添加剂存在下的电化学研究表明，钴络合物生成合成气，即 H 2和 CO的混合物，法拉第效率高达 >99%。 生成的 H 2 : CO的比例因添加剂而异。啊2 当使用 H 2 O 作为布朗斯台德酸添加剂时，会产生约 3 : 1 的 CO 比率。复合物的化学还原表明对四面体几何形状的扭曲，这可以通过 DFT 预测合理化，归因于具有 σ*(Co-S) 特征的轨道群。提出了一种机制方案，其中质子和 CO 2之间的竞争性结合决定了选择性。这项研究提供了对用于电化学合成气生产的将非无害配体与侧基部分结合的催化系统的开发的深入了解。

  DOI：

  10.1039/d0dt03270k

文献信息

• Synthesis of neutral iridium(III) and rhodium(III) complexes with the proligands Pri2P(C6H4SH-2) [priPSH]; PhP(C6H4SH-2)2 [phPS2H2] and PhP(C2H4SH)2 [ePS2H2]. The X-ray crystal structures of [Ir(priPS)3] and [Rh(H)(phPS2)(CO)(PPh3)]
  作者：David Morales-Morales、Sergio Rodrı́guez-Morales、Jonathan R. Dilworth、Antonio Sousa-Pedrares、Yifan Zheng

  DOI：10.1016/s0020-1693(02)00695-3

  日期：2002.4

  with iridium and rhodium precursors has been explored. By reacting IrCl3 with priPSH in the presence of NEt3 as base, the octahedral Ir(III) specie [Ir(priPS)3] was obtained and its crystal structure determined. Reactions of the potentially tridentated proligands phPS2H2 and ePS2H2 with trans-[MF(CO)(PPh3)2] (M=Rh and Ir) were also investigated. Complexes of general formula [M(H)(phPS2)(CO)(PPh3)] were

  摘要研究了杂磷-硫配体priPSH，phPS2H2和ePS2H2与铱和铑前体的反应性。在NEt3作为碱的存在下，通过使IrCl3与priPSH反应，获得八面体Ir（III）物种[Ir（priPS）3]，并确定了其晶体结构。还研究了潜在的三齿配体phPS2H2和ePS2H2与反式[MF（CO）（PPh3）2]（M = Rh和Ir）的反应。与phPS2H2得到通式[M（H）（phPS2）（CO）（PPh3）]的配合物。[Rh（H）（phPS2）（CO）（PPh3）]的单晶X射线结构测定表明该络合物为八面体。与脂族配体ePS2H2的反应提供了与具有phPS2H2的类似的物质。
• Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS) ₂ Complex
  作者：Rahul Jain、Mark S. Mashuta、Robert M. Buchanan、Craig A. Grapperhaus

  DOI：10.1002/ejic.201700590

  日期：2017.8.24

  Tetra-coordinate Ni(II) and Zn(II) complexes employing the PS chelates 2-(diphenylphosphino)benzenethiol (HL1) and 2-(diisopropylphosphino)benzenethiol (HL2) have been synthesized and characterized by spectroscopic, structural, and electrochemical methods. All complexes were screened for electrocatalytic activity for hydrogen evolution with acetic acid and hydrochloric acid and hyrdogen oxidation in

  采用 PS 螯合物 2-(二苯基膦基) 苯硫醇 (HL1) 和 2-(二异丙基膦基) 苯硫醇 (HL2) 的四配位 Ni(II) 和 Zn(II) 配合物已被合成，并通过光谱、结构和电化学方法进行表征。筛选所有配合物的电催化活性，用于在三乙胺存在下与乙酸和盐酸一起析氢和氢气氧化。镍配合物 Ni(L1)2 (1) 被发现从外部酸中还原质子，以 140 s-1 的周转频率在 1.09 V 的过电位下生成氢，并使用氧化还原活性碱三乙胺 (Et3N) 与在 0.33 V 的过电位下，周转频率为 23 s-1。Ni(L2)2 (3) 也被发现是二氢氧化的活性催化剂，但由于在电位窗口中无法还原 Ni (II/I)，因此质子还原效率低下。发现 Zn(L1)2 (2) 和 Zn(L2)2 (4) 配合物对于它们对这两种反应的电催化行为是不够的。
• Metal Complexes (M = Zn, Sn, and Pb) of 2-Phosphinobenzenethiolates: Insights into Ligand Folding and Hemilability
  作者：Brian M. Barry、Benjamin W. Stein、Christopher A. Larsen、Melissa N. Wirtz、William E. Geiger、Rory Waterman、Richard A. Kemp

  DOI：10.1021/ic400990n

  日期：2013.9.3

  The divalent metal complexes M-II(SC6H4-2-PR2)-kappa S-2,P}(2) (3-7, and 9-11) (M= Zn, Sn, or Pb; R = Pr-i, Bu-t, or. Ph); the Sn(W) complexes :Sn(SC6H4-2-PR2)-kappa(2)-S,P}Ph2Cl (12 and 13) (R = Pr-i and Bu-t), and the ionic Sn(IV) complexes [Sn(SC6H4-2-PR2)-kappa(2)-S,P}Ph-2[BPh4] (14 and 15) (R = Pr-i and Bu-t) have been prepared and characterized by multinuclear NMR spectroscopy and single. crystal X.-ray diffraction when suitable crystals were afforded The Sn(II) and Pb(II) complexes with R = Ph, Pr-i, or Bu-t (5, 6, 9, and 10) demonstrated ligand "folding" hinging on the P,S vector-a behavior driven by the repulsions of the metal/phosphorus and:metal/sulfur lone Pairs and increased M-S sigma bonding strength. This phenomenon Was examined by density functional theory (DFT) calculations for the compounds in both folded and unfolded states. The Sn(IV) compound 13 (R = Bu-t) crystallized with the phosphine in an axial position of the pseudotrigonal bipyramidal complex and also exhibited hemilability in the Sn P dative bond, while compound 12 (R = Pr-i), interestingly, crystallized with phosphine in an equatorial position and did not show hemilability. Finally, the crystal structure of 15 (R = Bu-t) revealed the presence of an uncommon, 4-coordinate, stable Sn(IV) cation.
• Electrocatalytic syngas generation with a redox non-innocent cobalt 2-phosphinobenzenethiolate complex
  作者：Nicholas M. Orchanian、Lorena E. Hong、David A. Velazquez、Smaranda C. Marinescu

  DOI：10.1039/d0dt03270k

  日期：——

  diselenolene systems. Electrochemical studies in the presence of 1 atm of CO2 and Brønsted acid additives indicate that the cobalt complex generates syngas, a mixture of H2 and CO, with faradaic efficiencies up to >99%. The ratios of H2 : CO generated vary based on the additive. A H2 : CO ratio of ∼3 : 1 is generated when H2O is used as the Brønsted acid additive. Chemical reduction of the complex indicates a

  合成了由 2-(二异丙基膦酰基) 苯硫醇配体负载的钴配合物，并对其电子结构和反应活性进行了研究。X 射线衍射研究表明，钴中心周围呈方形平面几何形状，膦配体呈反式排列。密度泛函理论计算和电子光谱测量表明混合金属-配体轨道特征，类似于先前研究的二硫烯和二硒烯系统。在 1 个大气压的 CO 2和布朗斯台德酸添加剂存在下的电化学研究表明，钴络合物生成合成气，即 H 2和 CO的混合物，法拉第效率高达 >99%。 生成的 H 2 : CO的比例因添加剂而异。啊2 当使用 H 2 O 作为布朗斯台德酸添加剂时，会产生约 3 : 1 的 CO 比率。复合物的化学还原表明对四面体几何形状的扭曲，这可以通过 DFT 预测合理化，归因于具有 σ*(Co-S) 特征的轨道群。提出了一种机制方案，其中质子和 CO 2之间的竞争性结合决定了选择性。这项研究提供了对用于电化学合成气生产的将非无害配体与侧基部分结合的催化系统的开发的深入了解。