| 155477-65-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 155477-65-9
• 化学式: BF₄*C₆₀H₄₁F₂₄P₄Ru
• 分子量: 1529.72
• InChiKey: JBCCERFUAUFHPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.68
• 重原子数：
  94.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  在 H₂ 作用下， 以 neat (no solvent, solid phase) 为溶剂， 生成
  参考文献：
  名称：

  Effect of the Ligand and Metal on the pKa Values of the Dihydrogen Ligand in the Series of Complexes [M(H2)H(L)2]+, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands, L

  摘要：

  The new dihydrogen complexes trans-[MH(H-2)L(2)]BF4, L = P(C6H4-4-R)(2)CH2CH2P(C6H4-4-R)(2), R = CF3, M = Fe, Ru, and Os, R = CH3, M = Fe, R = OMe, M = Ru, are prepared by reaction of the dihydride complexes MH(2)L(2) With HBF4. The H-H bond length of the spinning H-2 ligand does not change significantly as a function of R (from CF3 to CH3 when M = Fe and from CF3 to OCH3 for M = Ru) according to H-1 NMR T-1 and (1)J(HD) measurements while there is a lengthening for the Os complexes. The rate constants for H atom exchange (reflecting the ease of homolytic splitting of H-2) increase with the increasing donor ability of R for a given metal as do the pK(a) values (reflecting a decrease in ease of heterolytic splitting). The electrochemical properties of some complexes MH(Cl)L(2) and MH(2)L(2) are reported. As expected H-2 acidity decreases as the parent hydride becomes easier to oxidize with this change in R (same M). The trend in dihydrogen pK(a) values as a function of the metal, Fe < Os < Ru, is distinctively different to the trend in pK(a) values of the dihydride complexes M(H)(2)(CO)(4), Fe < Ru < Os, and [M(C5H5)(H)(2)(PPh(3))(2)](+), Ru < Os, The high H-H bond energy of the RU(2+) complexes trans-[RuH(H-2)L(2)]BF4 is probably the reason why they are less acidic than corresponding Os2+ complexes. A consideration of the pK(a) values correctly indicated that a RuH(2)L(2)/[RuH(H-2)L(2)](+) mixture would be more effective at H/D exchange between D-2 and HO(t)Bu than the dihydrogen complex alone.

  DOI：

  10.1021/ja00087a024
• 作为产物：
  描述：

  以 neat (no solvent) 为溶剂， 生成
  参考文献：
  名称：

  Effect of the Ligand and Metal on the pKa Values of the Dihydrogen Ligand in the Series of Complexes [M(H2)H(L)2]+, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands, L

  摘要：

  The new dihydrogen complexes trans-[MH(H-2)L(2)]BF4, L = P(C6H4-4-R)(2)CH2CH2P(C6H4-4-R)(2), R = CF3, M = Fe, Ru, and Os, R = CH3, M = Fe, R = OMe, M = Ru, are prepared by reaction of the dihydride complexes MH(2)L(2) With HBF4. The H-H bond length of the spinning H-2 ligand does not change significantly as a function of R (from CF3 to CH3 when M = Fe and from CF3 to OCH3 for M = Ru) according to H-1 NMR T-1 and (1)J(HD) measurements while there is a lengthening for the Os complexes. The rate constants for H atom exchange (reflecting the ease of homolytic splitting of H-2) increase with the increasing donor ability of R for a given metal as do the pK(a) values (reflecting a decrease in ease of heterolytic splitting). The electrochemical properties of some complexes MH(Cl)L(2) and MH(2)L(2) are reported. As expected H-2 acidity decreases as the parent hydride becomes easier to oxidize with this change in R (same M). The trend in dihydrogen pK(a) values as a function of the metal, Fe < Os < Ru, is distinctively different to the trend in pK(a) values of the dihydride complexes M(H)(2)(CO)(4), Fe < Ru < Os, and [M(C5H5)(H)(2)(PPh(3))(2)](+), Ru < Os, The high H-H bond energy of the RU(2+) complexes trans-[RuH(H-2)L(2)]BF4 is probably the reason why they are less acidic than corresponding Os2+ complexes. A consideration of the pK(a) values correctly indicated that a RuH(2)L(2)/[RuH(H-2)L(2)](+) mixture would be more effective at H/D exchange between D-2 and HO(t)Bu than the dihydrogen complex alone.

  DOI：

  10.1021/ja00087a024

文献信息

• Electrochemistry of transition metal hydride diphosphine complexes trans-MH(X)(PP)2 and trans-[MH(L)(PP)2]+, M = Fe, Ru, Os; PP = chelating phosphine ligand
  作者：Samantha D. Drouin、Patricia A. Maltby、Benjamin E. Rennie、Caroline T. Schweitzer、Adina Golombek、E. Paul Cappellani、Robert H. Morris

  DOI：10.1016/j.ica.2020.120124

  日期：2021.2

  over 30 iron, ruthenium, and osmium hydride phosphine complexes are reported, along with their MIII/II redox potentials. The complexes are of the type MH(PP)n(X) or [MH(PP)n(L)]+, where PP is one of the following bidentate phosphine ligands: dppe, dtpe, depe, and dtfpe, with n =2; or the tetradentate phosphine ligand meso-tet-1, with n = 1. The electrochemical data of these complexes and those from

  摘要报告了一系列30多种铁，钌和and氢化物膦配合物，以及它们的MIII / II氧化还原电位。络合物的类型为MH（PP）n（X）或[MH（PP）n（L）] +，其中PP是以下双齿膦配体之一：dppe，dtpe，depe和dtfpe，其中n = 2; 或n = 1的四齿膦配体meso-tet-1。这些配合物的电化学数据和文献中的数据用于确定铁和钌的氢化物配体的Lever EL参数为-0.65V。然而，对于来说，氢化物配体的EL值仅在-0.37 V时更正，这是由于相对论效应而导致的Os-Hσ键增强所致。该相关性适用于不可逆的氧化以及可逆的氧化。