chloro(1,1'-bis(diphenylphosphino)ferrocene)(pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate | 223242-63-5

• 英文名称: chloro(1,1'-bis(diphenylphosphino)ferrocene)(pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate
• 英文别名: [(η(5)-pentamethylcyclopentadienyl)RhCl(μ-1,1'-bis(diphenylphosphino)ferrocene-P,P')]PF6；[(1,2,3,4,5-pentamethylcyclopentadienyl)RhCl(Fe(η5-C5H4PPh2)2]PF6
• CAS: 223242-63-5
• 化学式: C₄₄H₄₃ClFeP₂Rh*F₆P
• 分子量: 972.943
• InChiKey: ZCZOSQWETZJBOD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  chloro(1,1'-bis(diphenylphosphino)ferrocene)(pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以60.1%的产率得到
  参考文献：
  名称：

  [Cp*Rh] 一氢化物的远程氧化激活**

  摘要：

  氧化还原化学：由螯合二膦配体支持的 [Cp*Rh] 配合物可以支持生成可分离的金属一氢化物，但之前的工作表明，促进这些配合物中 Rh−H 部分裂解所需的还原电位非常负。在此，[Cp*Rh] 一氢化物的以配体为中心的氧化被证明会导致 Rh-H 急剧酸化 23 p K a单位。因此，配体促进的氧化还原化学可以成为促进金属氢化物系统反应性的有用工具。

  DOI：

  10.1002/chem.202104389
• 作为产物：
  描述：

  1,1'-双(二苯基膦)二茂铁 、 sodium hexaflorophosphate 、 [(η(5)-pentamethylcyclopentadienyl)RhCl2]2(μ-1,1'-bis(diphenylphosphino)ferrocene)2 以 not given 为溶剂， 生成 chloro(1,1'-bis(diphenylphosphino)ferrocene)(pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate
  参考文献：
  名称：

  带有1,1'-双（二苯基膦甲基）二茂铁（dpmf）或1,1'-双（二苯基膦基）二茂铁（dppf）的（五甲基环戊二烯基）铑（III）配合物的制备和反应

  摘要：

  [Cp * RhCl 2 ] 2与1,1'-双（二苯基膦基甲基）二茂铁（dpmf）或1,1'-双（二苯基膦基）二茂铁（dppf）的反应得到桥联络合物[Cp * RnCl 2 ] 2（μ -diphos）（1：diphos = dpmf; 2：diphos = dppf）。在NaPF 6存在下与dppf反应，得到阳离子螯合的[Cp * RhCl（dppf- P，P '）]（PF 6）配合物3。在NaPF 6存在下，配合物1与二甲苯基异氰化物（XylNC）反应生成[Cp * 2 Rh 2 Cl 2（μ -dpmf）（XylNC）2 ]（PF 6）2，4，产量低。的[Cp *的Rh（dppf- P，P '）（MeCN中）]（PF 6）2，图5A，制备自3，的NaPF 6和硝酸银3在MeCN。在这种复杂的配位体的乙腈代替容易与路易斯碱（L），如CO和异氰化物，以形成的[Cp *的Rh（dppf- P，P

  DOI：

  10.1016/s0022-328x(98)00939-5

文献信息

• NO bond cleavage and various bonding modes of the nitrato ligand in rhodium complexes: syntheses and structures of [Cp*Rh(η1-NO3)(μ-Cl)]2, {[Cp*RhCl(PPh3)(CNC6H11)]2(NO2)(NO3)}·2H2O, [Cp*Rh(η1-NO3)(η1,μ-N3)]2, [Cp*Rh(η2-NO3)(O3SCF3)], trans-{[Rh(PPh3)2(CN2,6-Me2C6H3)2](NO3)}·H2O, and {[Cp*2Rh2(η2,μ-NO2-N,O)2(η1,μ-N3)](PF6)}·0.5H2O
  作者：Won Seok Han、Soon W Lee

  DOI：10.1016/s0020-1693(02)01466-4

  日期：2003.5

  The addition of 2 equiv. of AgNO3 to a dinuclear chloro-bridged Rh(III) compound, [Cp*RhCl2](2), resulted in the replacement of the terminal chloro ligand to give [Cp*Rh(eta(1)-NO3)(mu-Cl)](2) (1). On the other hand, the reaction of [Cp*RhCl2](2) with 4 equiv. of AgNO3 led to the formation of a mononuclear bis(nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(2)-NO3)] (2). Compound 1 reacted With PPh3 and cyclohexyl isocyanide (CN-C6H11) to give a chiral compound, [Cp*RhCl(PPh3)(CN-C6H11)](2)(NO2)(NO3)} 2H(2)O (3.2H(2)O), which shows an unusual example of the nitrate-to-nitrite reduction in the rhodium coordination sphere. The reaction of compound 2 with either NaN3 or N3SiMe3 gave a dinuclear (eta(1)-nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(1),mu-N-3)](2) (4). On the other hand, on addition of silver triflate (AgOTf), compound 2 underwent replacement to give a monormclear (eta(2)-nitrato)-rhodium compound, [Cp*Rh(eta(2)-NO3)(OTf)] (5). In addition, compound 2 reacted with a mixture of PPh3 and 2,6-dimethylphenyl isocyanide (CN-2,6-Me2C6H3) to give trans-[Rh(PPh3)(2)(CN-2,6-Me2C6H3)(2)](NO3)} . H2O (6. H2O), Which exhibits the complete elimination of all ligands in compound 2 and indicates the formal reduction of the rhodium metal from + 3 to + 1. The nitro-rhodium compound, [Cp-2*Rh-2(eta(2), mu-NO2-N,O)(2)(eta(1),mu-N-3)](PF6)} . 0.5H(2)O (7 . 0.5H(2)O), was prepared by the reaction of [Cp*RhCl(dppf)](PF6) (dppf = Fe(eta(5) -C5H4PPh2)(2)) with a mixture of N3SiMe3 and AgNO3, Which also displays the N-O bond cleavage of nitrate (NO3-) to nitrite (NO2-). The structures of 1, 3 . 2H(2)O, 4, 5, 6 - HO, and 7 . 0.5H(2)O were determined by X-ray diffraction. (C) 2002 Elsevier Science B.V. All rights reserved.
• Azido[1,1′-bis(diphenylphosphino)ferrocene](pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate
  作者：Won Seok Han、Soon W. Lee

  DOI：10.1107/s0108270104004779

  日期：2004.4.15

  In the title compound, azido-2kappaN-bis[mu-(1eta(5): 2kappaP)-diphenylphosphinocyclopentadienyl][ 2(eta(5))-pentamethylcyclopentadienyl] iron(III) rhodium(III) hexafluorophosphate, [Rh(C10H15)( N-3)}Fe(mu-C17H14P)(2)}] PF6 or [FeRh(C10H15)(mu-C17H14P)(2)(N-3)] PF6, the coordination sphere of Rh-III can be described as pseudo-tetrahedral, composed of two P atoms from a 1,1'-bis( diphenylphosphino) ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C5Me5 (Cp*) ligand. The two cyclopentadienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh...Fe distance is 4.340 (2) Angstrom.