dichloro[1,4-bis(diphenylphosphino)-1,2,3,4-tetraethyl-1,3-butadiene]platinum | 675825-03-3

• 英文名称: dichloro[1,4-bis(diphenylphosphino)-1,2,3,4-tetraethyl-1,3-butadiene]platinum
• CAS: 675825-03-3
• 化学式: C₃₆H₄₀Cl₂P₂Pt
• 分子量: 800.647
• InChiKey: FOGXFQYZMNPHFX-HYWVMSBSSA-L

反应信息

• 作为反应物：
  描述：

  S-1,1'-联-2-萘酚 、 dichloro[1,4-bis(diphenylphosphino)-1,2,3,4-tetraethyl-1,3-butadiene]platinum 在 sodium tert-butoxide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以88%的产率得到[(1,4-bis(diphenylphosphino)-1,2,3,4-tetraethyl-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
• 作为产物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 1,4-bis(diphenylphosphino)-1,2,3,4-tetraethyl-1,3-butadiene 以 二氯甲烷 为溶剂， 以82%的产率得到dichloro[1,4-bis(diphenylphosphino)-1,2,3,4-tetraethyl-1,3-butadiene]platinum
  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