((triphos)Rh(μ-S)2Rh(triphos))(BPh4)2 | 105139-43-3

• 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: ((triphos)Rh(μ-S)2Rh(triphos))(BPh4)2
• 英文别名: [(triphos)HRh(μ-S)2Rh(triphos)](BPh4)2
• CAS: 105139-43-3
• 化学式: 2C₂₄H₂₀B*C₈₂H₇₈P₆Rh₂S₂
• 分子量: 2157.77
• InChiKey: JPZNMUXYLBJPTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.14
• 重原子数：
  117.0
• 可旋转键数：
  16.0
• 环数：
  23.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  ((triphos)Rh(μ-S)2Rh(triphos))(BPh4)2 在 O₂ 作用下， 以 二氯甲烷 为溶剂， 以>99的产率得到
  参考文献：
  名称：

  Bianchini, Claudio; Mealli, Carlo; Meli, Andrea, Inorganic Chemistry, 1986, vol. 25, # 26, p. 4617 - 4618

  摘要：

  DOI：
• 作为产物：
  描述：

  ((triphos)Rh(S2CO))BPh4 在 NaB(C₆H₅)4 、 HSO₃CF₃ or 、 CH₃SO₃CF₃ 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 以78%的产率得到((triphos)Rh(μ-S)2Rh(triphos))(BPh4)2
  参考文献：
  名称：

  Bianchini, Claudio; Meli, Andrea; Laschi, Franco, Inorganic Chemistry, 1989, vol. 28, # 2, p. 227 - 233

  摘要：

  DOI：

文献信息

• Metal-assisted three-fragment demolition of the dithiocarbonate ligand: a new synthetic route to homo- and heterobinuclear bis(.mu.-sulfido)metal complexes. Chemical, electrochemical, and spectroscopic characterization of a family of complexes of iron, cobalt, rhodium, and platinum with bridging sulfido ligands
  作者：Claudio. Bianchini、Andrea. Meli、Franco. Laschi、Alberto. Vacca、Piero. Zanello

  DOI：10.1021/ja00220a032

  日期：1988.6

  Preparation des complexes de formule generale [(triphos) Rh(μ-S) 2 M(L)] (BPh 4 ) x (M=Rh, Co, Pt ou Fe; L=diphos, triphos ou etriphos). Donnees IR, RMN et RPE

  [(triphos) Rh(μ-S) 2 M(L)] (BPh 4 ) x (M=Rh, Co, Pt ou Fe; L=diphos, triphos, triphos ou etriphos)制备复合物通用公式。Donnees IR、RMN 和 RPE
• Activation of Molecular Hydrogen over a Binuclear Complex with Rh₂S₂ Core:  DFT Calculations and NMR Mechanistic Studies
  作者：Andrea Ienco、Maria José Calhorda、Joachim Reinhold、Francesca Reineri、Claudio Bianchini、Maurizio Peruzzini、Francesco Vizza、Carlo Mealli

  DOI：10.1021/ja047992j

  日期：2004.9.1

  The dicationic complex [(triphos)Rh(mu-S)(2)Rh(triphos)](2+), 1 (modeled as 1 c) [triphos = CH3C(CH2PPh2)(3)], is known to activate two dihydrogen molecules and produce the bis(mu-hydrosulfido) product [(triphos)(H)Rh(mu-SH)(2)Rh(H)(triphos)](2+), 2 (modeled as 2b), from which 1 is reversibly obtained. The possible steps of the process have been investigated with DFT calculations. It has been found that each d(6) metal ion in 1c, with local square pyramidal geometry, is able to anchor one H-2 molecule in the side-on coordination. The step is followed by heterolytic splitting of the H-H bond over one adjacent and polarized Rh-S linkage. The process may be completed before the second H2 molecule is added. Alternatively, both H-2 molecules are trapped by the Rh2S2 core before being split in two distinct steps. Since the ambiguity could not be solved by calculations, P-31 and H-1 NMR experiments, including para-hydrogen techniques, have been performed to identify the actual pathway. In no case is there experimental evidence for any Rh-(eta(2)-H-2) adduct, probably due to its very short lifetime. Conversely, 1H NMR analysis of the hydride region indicates only one reaction intermediate which corresponds to the monohydride-mu-hydrosulfide complex [(triphos)Rh(H)(mu-SH)(u-S)Rh(triphos)](2+) (3) (model 5a). This excludes the second hypothesized pathway. From an energetic viewpoint the computational results support the feasibility of the whole process. In fact, the highest energy for H-2 activation is 8.6 kcal mol(-1), while a larger but still surmountable barrier of 34.6 kcal mol(-1) is in line with the reversibility of the process.y
• Bianchini, Claudio; Mealli, Carlo; Meli, Andrea, Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 425 - 428
  作者：Bianchini, Claudio、Mealli, Carlo、Meli, Andrea、Peruzzini, Maurizio、Vizza, Francesco

  DOI：——

  日期：——