1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene | 348582-89-8

• 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: 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene
• 英文别名: (5-diphenylphosphanyl-3,4-dimethylhexa-2,4-dien-2-yl)-diphenylphosphane
• CAS: 348582-89-8
• 化学式: C₃₂H₃₂P₂
• 分子量: 478.554
• InChiKey: RVUIMXUXICCLFI-UHFFFAOYSA-N

物化性质

• 沸点：
  619.4±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.84
• 重原子数：
  34.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene 在 sodium tert-butoxide 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 生成 [(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)]
  参考文献：
  名称：

  Comparative Study of Diastereoisomer Interconversion in Chiral BINOL-ate and Diamine Platinum Complexes of Conformationally Flexible NUPHOS Diphosphines

  摘要：

  A thorough and detailed study of diastereointerconversion in the chiral platinum complexes [(NUPHOS)Pt{(S)-BINOL}] (3a-e) has been undertaken and compared with the results of a similar study with [(BIPHEP)Pt{(S)-BINOL}]. Rate data revealed that this process obeys first-order relaxation kinetics, and rate constants for conversion of the minor to the major diastereoisomer have been obtained. Eyring analysis of the data gave DeltaH(double dagger) and DeltaS(double dagger) values of 22-25 kcal mol(-1) and -1 to -16 eu, respectively. In combination with computational analysis, these studies indicate that atropinversion most likely occurs via an on-metal pathway involving a planar seven-membered transition state. Substitution of (S)-BINOL for (S,S)-DPEN results in a marked reduction in the barrier to atropinversion; a DeltaH(double dagger) value of 17 kcal mol(-1) has been determined for the conversion of delta-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2 to lambda-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2, which could indicate that an alternative mechanism operates.

  DOI：

  10.1021/om034289f

文献信息

• Ruthenium Complexes of the 1,4-Bis(diphenylphosphino)-1,3-butadiene-Bridged Diphosphine 1,2,3,4-Me₄-NUPHOS:  Solvent-Dependent Interconversion of Four- and Six-Electron Donor Coordination and Transfer Hydrogenation Activity
  作者：Simon Doherty、Colin R. Newman、Christopher Hardacre、Mark Nieuwenhuyzen、Julian G. Knight

  DOI：10.1021/om020861b

  日期：2003.3.1

  In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.