{pentamethylcyclopentadienylrhodium(III)(PPh2H)Cl2} | 112654-38-3

• 英文名称: {pentamethylcyclopentadienylrhodium(III)(PPh2H)Cl2}
• CAS: 112654-38-3
• 化学式: C₂₂H₂₆Cl₂PRh
• 分子量: 495.234
• InChiKey: IFLFVUJPTGIEBQ-UHFFFAOYSA-L

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：

  {pentamethylcyclopentadienylrhodium(III)(PPh2H)Cl2} 在 二乙胺 作用下， 以 丙酮 为溶剂， 生成 bis(pentamethylcyclopentadienyl)dirhodium(II)(μ-diphenylphosido)(μ-Cl) 、 bis(pentamethylcyclopentadienyl)dirhodium(II)bis(μ-diphenylphosphido)
  参考文献：
  名称：

  SYNTHESE UNDreaktivität冯[C 5我5的Rh（μ-PME 2）] 2：Additions- UND insertionsreaktionen冯sauerstoff UND seinen homologen一个管芯的Rh 2 P 2 -einheit

  摘要：

  [C 5我5的Rh（μ-PME 2）2 ]（I）已被从[C制备5我5的RhCl 2 ] 2通过C 5我5的Rh（PME 2 2H）氯2（II）作为中间。配合物I与氧及其同系物E n（E = O，S，Se，Te）反应形成三种不同类型的产物（VII–XI），其起源是将E添加到RhRh中或将E插入一个或两个RhP键。I用CF 3 CO 2 H / NH 4 PF 6质子化产生[（C 5 Me5 RH）2（μ-H）（μ-PME 2）2 ] PF 6（VI）。的[C合成5我5的Rh（μ-PPH 2）] 2还描述了（XIII）。

  DOI：

  10.1016/0022-328x(83)80097-7
• 作为产物：
  描述：

  [Rh(Cp*)Cl2(diphenyl-perfluorooctanoylphosphine)] 以 neat (no solvent, solid phase) 为溶剂， 生成 {pentamethylcyclopentadienylrhodium(III)(PPh2H)Cl2}
  参考文献：
  名称：

  合成和过渡金属化学“phosphomide”配位体：的反应性和二苯基的电子性质的比较P -全氟辛酰基膦，P -乙酰基二苯基膦和P -anisoyl -二苯基膦。[RHCP *（PH的X射线晶体结构2 PC（O）CH 3）氯2 ]

  摘要：

  据报道，可以从仲膦方便地合成几个“磷化物”配体（P与羰基相邻）。通过对相应的羰基铑配合物反式-[RhL 2（CO）Cl ）的ν（CO）的测定，新的异戊基取代的膦具有相当好的水解稳定性，并且是比P-乙酰基-二苯基膦更强的σ供体配体。]。相反，发现衍生自全氟辛酰氯的新的磷酰亚胺是高度不稳定的，电子贫乏的π受体配体。[RhCp * Cl 2 {Ph 2 PC（O）CH 3 }]的晶体结构显示正常伪-八面体钢琴凳的分子几何，RhP键长为2.3186（5）Å。观察到的对-戊基磷酰亚胺的额外稳定性使我们首次将这类配体应用于铑催化的加氢甲酰化反应中。

  DOI：

  10.1016/s0022-328x(02)02152-6

文献信息

• Heteronuclear and heterovalent diphenylphosphido-bridged complexes of rhodium, iridium and ruthenium. Crystal structure of [(C5Me5)ClRh(μ-Cl)(μ-PPh2)Rh(COD)] · Et2O (COD = 1,5-cyclooctadiene)
  作者：Montserrat Esteban、Alberto Pequerul、Daniel Carmona、Fernando J. Lahoz、Alberto Martín、Luis A. Oro

  DOI：10.1016/0022-328x(91)86254-n

  日期：1991.1

  Mononuclear complexes of formulae [LMCl2(HPRR′)], [LCMl(HPR2)2]BF4 and [LM(acac)(HPR2)]BF4 (M = Rh, Ir; L = C5Me5. M = Ru; L = p-Cymene; R = Ph, H; R′ = H; Hacac = acetylacetone, but not in all possible combinations) have been prepared from the corresponding [(LMCl}2(μ-Cl)2] or [LMCl(acac)] and HPRR′. Complexes [LMCl2(HPPh2)] [L = C5Me5; M = Rh (I), Ir (IV), L = p-Cymene; M = Ru (VII)] react with [M′(μ-OMe)(diolefin)]2

  式[LMCl 2（HPRR'）]，[LCM1（HPR 2）2 ] BF 4和[LM（acac）（HPR 2）] BF 4的单核络合物（M = Rh，Ir; L = C 5 Me 5。 M = Ru; L =对-Cymene; R = Ph，H; R'= H; Hacac =乙酰丙酮，但不是所有可能的组合）都是由相应的[（LMCl} 2（μ-Cl）2）制备的[LMCl 2（HPPh 2）] [L = C 5 Me 5 ; M = Rh（I），Ir（IV），L = p- Cymene; M = Ru （VII）]与[M'（μ-OMe）（二烯烃）]反应2（M'= RH;二烯烃= tetrafluorobenzobarrelene（TFB），1,5-环辛二烯（COD）M'= IR;二烯烃= COD），得到式diphenylphosphido桥连的络合物[LMCl 2（μ-PPH 2）M ′（二烯烃）]。的结构[（C
• Binuclear pentamethylcyclopentadienyl dirhodium complexes with pyrazolato and diphenylphosphido bridging ligands
  作者：Daniel Carmona、M. Pilar Lamata、Montserrat Esteban、Fernando J. Lahoz、Luis A. Oro、M. Carmen Apreda、Concepci�n Foces-Foces、F�lix H. Cano

  DOI：10.1039/dt9940000159

  日期：——

  The reaction of [Rh(C(5)Me(5))}(2)(mu-L)(mu-OMe)(2)]BF4 [L = pyrazolate (pt), 3-methylpyrazolate. 3,5-dimethylpyrazolate or 3(5)-bromo-5(3)-methylpyrazolate] with HPPh(2) has been studied. Complexes of general formulae [Rh(C(5)Me(5))}2(mu-L)(mu-OH)(mu-PPh(2))]BF4, [Rh(C(5)Me(5))}(2)(mu-L)(-PPh(2))2]BF4 and [Rh(C(5)Me(5))}(2)(mu-OH)(2)(mu-PPh(2))]BF4 were prepared and characterized by analytical and spectroscopic means. The crystal structure of [Rh(C(5)Me(5))}(2)(mu-pz)(mu-PPh(2))(2)]BF4 . CHCl3 was determined. The rhodium atoms show pseudo-octahedral geometry and are separated by 3.473(1) Angstrom. The mu-hydroxo complexes [Rh(C(5)Me(5))}(2)(mu-L)(mu-OH)(mu-PPh(2))]BF4 react with hydrochloric acid affording the corresponding mu-chloride compounds [Rh(C(5)Me(5))}(2)(mu-L)(mu-Cl)(mu-PPh(2))]BF4, which in turn have been also prepared from [Rh(C(5)Me(5))}(2)(mu-OH)(3)]BF4, HL, HPPh(2) and HCl in 1:1:1:1 ratio. The crystal structure of [Rh(C(5)Me(5))}2(mu-pz)(mu-Cl)(mu-PPh(2))]BF4 . CHCl3 has been determined. Two (C(5)Me(5))Rh moieties are connected by three different anionic ligands, pz, Cl and PPh(2). The rhodium atoms are separated by 3.432(1) Angstrom. Aged solutions of reaction mixtures of [Rh(C(5)Me(5))}(2)(mu-L)(mu-OMe)(2)]BF4 and HPPh(2) contain [Rh(C(4)Me(5))}(2)(mu-Ph(2)PO(2))(2)(mu-PPh(2))]BF4, the diphenylphosphinato ligands arising from Ph(2)P(O)OH, an oxidation product of HPPh(2). The crystal structure of the solvate has been established. Two Ph(2)PO(2) groups and a PPh(2) ligand bridge two (C(5)Me(5))Rh units. The rhodium-rhodium distance is 4.049(1) Angstrom. The mu-hydrido complex [Rh(C(5)Me(5))}(2)(mu-H)(mu-pz)(mu-PPh(2))] has been prepared by treating [Rh(C(5)Me(5))}(2)(mu-OH)(3)]BF4 with Hpz and HPPh(2) in refluxing propan-2-ol.
• Werner, Helmut; Klingert, Bernd; Rheingold, Arnold L., Organometallics, 1988, vol. 7, # 4, p. 911 - 917
  作者：Werner, Helmut、Klingert, Bernd、Rheingold, Arnold L.

  DOI：——

  日期：——