bis[2-(diisopropylphosphanyl)benzenethiolato]zinc(II) | 1449605-28-0

• 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: bis[2-(diisopropylphosphanyl)benzenethiolato]zinc(II)
• 英文别名: Zn{(SC₆H₄-2-PⁱPr₂)-κ²-S,P}₂；Zn(2-(diisopropylphosphanyl)benzenethiolato)₂；zinc;2-di(propan-2-yl)phosphanylbenzenethiolate
• CAS: 1449605-28-0
• 化学式: C₂₄H₃₆P₂S₂Zn
• 分子量: 516.019
• InChiKey: UDODWAKJFSRAOR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.03
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  氯二异丙基膦 在 正丁基锂 、 四甲基乙二胺 、 三乙胺 作用下， 以 甲醇 、 环己烷 为溶剂， 反应 15.0h， 生成 bis[2-(diisopropylphosphanyl)benzenethiolato]zinc(II)
  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

文献信息

• 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。