{Ru2(SH)(CO)5(μ-((CH3)2CHO)2PN(C2H5)P(OCH(CH3)2)2)2}{SbF6} | 151966-49-3

• 英文名称: {Ru2(SH)(CO)5(μ-((CH3)2CHO)2PN(C2H5)P(OCH(CH3)2)2)2}{SbF6}
• CAS: 151966-49-3
• 化学式: C₃₃H₆₇N₂O₁₃P₄Ru₂S*F₆Sb
• 分子量: 1293.74
• InChiKey: AXMGXBAJMHMEAN-UHFFFAOYSA-G

反应信息

• 作为反应物：
  描述：

  {Ru2(SH)(CO)5(μ-((CH3)2CHO)2PN(C2H5)P(OCH(CH3)2)2)2}{SbF6} 在 KOH 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到{Ru2(μ-S)(CO)4(μ-((CH3)2CHO)2PN(C2H5)P(OCH(CH3)2)2)2}
  参考文献：
  名称：

  Oxidation of diphosphazane-bridged derivatives of diruthenium nonacarbonyl by silver(I) salts in protic solvents: synthesis, structural characterization and protonation of the adduct [Ru₂{µ-η²-OC(O)}(CO)₄{µ-(RO)₂PN(Et)P(OR)₂}₂](R = Me or Prⁱ) involving a novel mode of co-ordination of carbon dioxide

  摘要：

  Treatment of [Ru2(mu-CO)(CO),{mu-(RO)2PN(Et)P(OR)2)2] (R = Me or Pr(i)) with AgSbF6 in methanol, ethanol or tetrahydrofuran-water resulted in the formation of the solvento species [Ru2(CO)5(R'OH){mu-(RO)2PN(Et)P(OR)2}2] [SbF6]2 which is isolable for R' = H but which spontaneously deprotonatesto the alkoxycarbonyl-bridged derivative [Ru2{mu-eta2-OC(OR')}(CO)4{mu-(RO)2PN(Et)P(OR)2}2]SbF6 for R' = Me or Et. The aqua species [Ru2(CO)5(H2O){mu-(RO)2PN(Et)P(OR)2}2] [SbF6], was readily deprotonated in consecutive steps by appropriate bases to afford respectively the hydroxycarbonyl-bridged species [Ru2{mu-eta2-OC(OH)}(CO)4{p-(RO)2PN(Et)P(OR)2}2]SbF6 and the adduct [Ru2{mu-eta2-OC(O)}(CO)4{mu-(RO)2PN(Et)P(OR)2}2] in which the carbon dioxide molecule adopts a novel bridging co-ordination mode; this deprotonation is reversible and treatment of the latter with HBF4.OEt2 leads to stepwise regeneration of the aqua species. The co-ordinated water molecule in [Ru2(CO)5(H2O){mu-(PriO)2PN(Et)P(OPri)2)2] [SbF6]2 was readily displaced by acids HA derived from conjugate bases with potential co-ordinating properties such as thiolate ions R''S- (R'' = H or Ph) or carboxylate ions R'''CO2- (R''' = H, Me, Ph or CF3), to produce monocationic pentacarbonyl species of the type [Ru2A(CO)5{mu-(PriO)2PN(Et)P(OPri)2)2]SbF6, detection of an intermediate, presumably [RU2(CO)5-(HA){mu-(PriO)2PN(Et)P(OPri)2}2] [SbF6]2, was possible for HA = HCO2H and MeCO2H. The sulfido derivatives [RU2(SR'')(CO)5{mu-(PriO)2PN(Et)P(OPri)2}2]SbF6 (R'' = H or Ph) rapidly decarbonylate in solution to afford the tetracarbonyl products [RU2(mu-SR'')(CO)4{mu-(PriO) 2PN(Et)P(OPri)2}2]SbF6 in which the sulfido group bridges the two ruthenium atoms. On the other hand the carboxylato derivatives [Ru2{OC(O)R'''}(CO)5{mu-(PriO)2PN(Et)P(OPri)2}2]SbF6 (R''' = H, Me, Ph or CF3) are stable to decarbonylation in solution at room or elevated temperatures but can be decarbonylated to the carboxylato-bridged products [Ru2{mu-eta2-OC(R''')O}(CO)4{mu-(PriO)2PN(Et)P(OPri)2}2]SbF6 by irradiation with ultraviolet light. The water molecule in [Ru2(CO)5(H2O){mu-(PriO)2PN(Et)P(OPri)2}2]-[SbF6]2 was also readily displaced by the conjugate bases of the above acids HA, but in contrast to that observed for the carboxylic acids R'''CO2H (R''' = H, Me or Ph), reaction of the aqua species with the corresponding carboxylate ions R'''CO2- led to direct formation of the carboxylato-bridged species [Ru2{mu-eta2-OC(R''')O}(CO)4(mu-(PriO)2PN(Et)P(OPri)2}2]SbF6. Possible mechanisms for the formation of the various products are discussed as are the structures of [Ru2(CO)5(H2O){mu-(PriO)2PN(Et)P(OPri)2}2][SbF6]2.OCMe2, [RU2{mu-eta2-OC(OEt)}(CO)4{mu-(MeO)2PN(Et)P(OMe)2}2]SbF6, [Ru2{mu-eta2-OC(Me)O}(CO)4{mu-(PriO)2PN(Et)P(OPri)2}2]PF6 and [RU2{mu-eta2-OC(O)}(CO)4{mu-(PriO)2-PN(Et)P(OPri)2}2], established X-ray crystallographically.

  DOI：

  10.1039/dt9930002735
• 作为产物：
  描述：

  {Ru2(CO)4(H2O)(μ-((CH3)2CHO)2PN(C2H5)P(OCH(CH3)2)2)2}{SbF6}2 在 hydrogen sulfide 作用下， 以 丙酮 为溶剂， 生成 {Ru2(SH)(CO)5(μ-((CH3)2CHO)2PN(C2H5)P(OCH(CH3)2)2)2}{SbF6}
  参考文献：
  名称：

  Oxidation of diphosphazane-bridged derivatives of diruthenium nonacarbonyl by silver(I) salts in protic solvents: synthesis, structural characterization and protonation of the adduct [Ru₂{µ-η²-OC(O)}(CO)₄{µ-(RO)₂PN(Et)P(OR)₂}₂](R = Me or Prⁱ) involving a novel mode of co-ordination of carbon dioxide

  摘要：

  Treatment of [Ru2(mu-CO)(CO),{mu-(RO)2PN(Et)P(OR)2)2] (R = Me or Pr(i)) with AgSbF6 in methanol, ethanol or tetrahydrofuran-water resulted in the formation of the solvento species [Ru2(CO)5(R'OH){mu-(RO)2PN(Et)P(OR)2}2] [SbF6]2 which is isolable for R' = H but which spontaneously deprotonatesto the alkoxycarbonyl-bridged derivative [Ru2{mu-eta2-OC(OR')}(CO)4{mu-(RO)2PN(Et)P(OR)2}2]SbF6 for R' = Me or Et. The aqua species [Ru2(CO)5(H2O){mu-(RO)2PN(Et)P(OR)2}2] [SbF6], was readily deprotonated in consecutive steps by appropriate bases to afford respectively the hydroxycarbonyl-bridged species [Ru2{mu-eta2-OC(OH)}(CO)4{p-(RO)2PN(Et)P(OR)2}2]SbF6 and the adduct [Ru2{mu-eta2-OC(O)}(CO)4{mu-(RO)2PN(Et)P(OR)2}2] in which the carbon dioxide molecule adopts a novel bridging co-ordination mode; this deprotonation is reversible and treatment of the latter with HBF4.OEt2 leads to stepwise regeneration of the aqua species. The co-ordinated water molecule in [Ru2(CO)5(H2O){mu-(PriO)2PN(Et)P(OPri)2)2] [SbF6]2 was readily displaced by acids HA derived from conjugate bases with potential co-ordinating properties such as thiolate ions R''S- (R'' = H or Ph) or carboxylate ions R'''CO2- (R''' = H, Me, Ph or CF3), to produce monocationic pentacarbonyl species of the type [Ru2A(CO)5{mu-(PriO)2PN(Et)P(OPri)2)2]SbF6, detection of an intermediate, presumably [RU2(CO)5-(HA){mu-(PriO)2PN(Et)P(OPri)2}2] [SbF6]2, was possible for HA = HCO2H and MeCO2H. The sulfido derivatives [RU2(SR'')(CO)5{mu-(PriO)2PN(Et)P(OPri)2}2]SbF6 (R'' = H or Ph) rapidly decarbonylate in solution to afford the tetracarbonyl products [RU2(mu-SR'')(CO)4{mu-(PriO) 2PN(Et)P(OPri)2}2]SbF6 in which the sulfido group bridges the two ruthenium atoms. On the other hand the carboxylato derivatives [Ru2{OC(O)R'''}(CO)5{mu-(PriO)2PN(Et)P(OPri)2}2]SbF6 (R''' = H, Me, Ph or CF3) are stable to decarbonylation in solution at room or elevated temperatures but can be decarbonylated to the carboxylato-bridged products [Ru2{mu-eta2-OC(R''')O}(CO)4{mu-(PriO)2PN(Et)P(OPri)2}2]SbF6 by irradiation with ultraviolet light. The water molecule in [Ru2(CO)5(H2O){mu-(PriO)2PN(Et)P(OPri)2}2]-[SbF6]2 was also readily displaced by the conjugate bases of the above acids HA, but in contrast to that observed for the carboxylic acids R'''CO2H (R''' = H, Me or Ph), reaction of the aqua species with the corresponding carboxylate ions R'''CO2- led to direct formation of the carboxylato-bridged species [Ru2{mu-eta2-OC(R''')O}(CO)4(mu-(PriO)2PN(Et)P(OPri)2}2]SbF6. Possible mechanisms for the formation of the various products are discussed as are the structures of [Ru2(CO)5(H2O){mu-(PriO)2PN(Et)P(OPri)2}2][SbF6]2.OCMe2, [RU2{mu-eta2-OC(OEt)}(CO)4{mu-(MeO)2PN(Et)P(OMe)2}2]SbF6, [Ru2{mu-eta2-OC(Me)O}(CO)4{mu-(PriO)2PN(Et)P(OPri)2}2]PF6 and [RU2{mu-eta2-OC(O)}(CO)4{mu-(PriO)2-PN(Et)P(OPri)2}2], established X-ray crystallographically.

  DOI：

  10.1039/dt9930002735