trans-RhCl(CO)(PEt2Ph)2 | 15691-93-7

• 英文名称: trans-RhCl(CO)(PEt2Ph)2
• CAS: 15691-93-7；29553-46-6
• 化学式: C₂₁H₃₀ClOP₂Rh
• 分子量: 498.775
• InChiKey: XFFYFQDFBFPYQL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  trans-RhCl(CO)(PEt2Ph)2 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Alkene and dihydrogen formation by catalytic dehydrogenation of alkane with RhCl(pr3)2 photogenerated from rhcl(co)(pr3)2

  摘要：

  DOI：

  10.1016/0304-5102(89)80138-5
• 作为产物：
  描述：

  di-μ-chloro-bis[bis(cyclo-octene)rhodium] 、 二乙基苯膦 在 CO 作用下， 以 light petroleum 为溶剂， 以85%的产率得到trans-RhCl(CO)(PEt2Ph)2
  参考文献：
  名称：

  Preparation and reactivity of iodomethyl complexes of rhodium(III); crystal and molecular structure of carbonylchloroiodo(iodomethyl)bis(triethylphosphine)rhodium(III)

  摘要：

  Diiodomethane oxidatively added to [RhCl(CO)(PR3)2] formed [RhCl(I)(CH2I)(CO)(PR3)2] for R3 = Me3, Et3 or Et2Ph but not for R3 = EtPh2, Ph3, (C6H11)3 or (OMe)3; CH2Br2 gave a mixture of bromo- and chloromethyl complexes whilst CH2ICl gave two isomers of [RhCl(I)(CH2Cl)(CO)(PEt3)2] with I Cl trans to CH2Cl. In polar solvents or on treatment with water or MeOH, [RhCl(I)(CH2I)(CO)(PEt3)2] underwent a halide-scrambling reaction to give several compounds containing CH2I or CH2Cl ligands which have been identified spectroscopically. The same scrambling occurs under high pressures of CO, although IR, NMR and model studies suggest the Rh-C(O)CH2X species are also formed by insertion of CO into the Rh-CH2X bond. Most of the acyl products are unstable to loss of ketene, but one may be stable [nu(C=O) 1665 cm-1]. The complex [RhCl(I)(CH2I)(CO)(PEt3)2] has been characterised crystallographically: triclinic, space group P1BAR, a = 12.343(3), b = 14.327(2), c = 1 5.426(2) angstrom, alpha = 11 3.78(1), beta = 67.25(1), gamma = 90.20(1)degrees, Z = 4, R = 0.0453. Each unit cell contains two pairs of molecules differing in the relative orientations of one PEt3 ligand. In both cases, Rh-C [2.080(6), 2.063(9) angstrom], C-I [2.151(9), 2.121 (10) angstrom] and Rh-C-I [119.9(5), 120.3(4)degrees] are similar to those reported for related compounds. Both molecules have mutually trans phosphines and CH2I trans to I.

  DOI：

  10.1039/dt9940001963

文献信息

• Substitution of CO by picolines and amines in RhCl(CO)(PR3)2. Synthesis and crystal structure of cis-RhCl(3-pic){P(OPh)3}2
  作者：A.M. Trzeciak、J.J. Ziólkowski、T. Lis

  DOI：10.1016/0022-328x(91)80251-e

  日期：1991.1

  = cycloocta-1,5-diene) or RhCl(CO)P(OPh)3}2 with amines. CO substitution by amines RhCl(CO)(PR3)2 complexes [PR3 = P(OMe)3, P(OPh)3, P(O-o-MeC6H4)3, P(O-m-MeC6H4)3, PEt2Ph, PEtPh2, PMe2Ph, PMePh2 or PPh3] is limited by steric properties of amine and PR3 ligands. 3-Picoline substitutes CO only in complexes with PR3 ligands with cone angle γ ⩽ 140° [16]. The rate of CO substitution by 2-picoline is less

  标题复杂，顺式的RhCl（3-PIC）P（OPH）3 } 2（3-PIC = 3吡啶），已经制备具有两个其他同构铑配合物，分别与4-甲基吡啶和CH 2 CH CH 2 NH 2。RhCl（3-PIc）P（OPh）3 } 2化合物在空间群P中结晶，a = 10.531（6），b = 12.025（9），c = 15.943（8），α= 83.01（5） ，β= 79.46（4），γ= 86.33（5）°；Z =2。在[Rh（μ-OMe）（cod）] 2，[Rh（μ-Cl）（cod）]的反应中获得了RhCl（胺）P（OPh）3 } 2配合物。2（cod =环辛-1,5-二烯）或RhCl（CO）P（OPh）3 } 2与胺。通过胺RhCl（CO）（PR 3）2络合物[PR 3 = P（OMe）3，P（OPh）3，P（O- o- MeC 6 H 4）3，P（O- m -MeC 6 H 4）3，PEt
• Photocatalytic dehydrogenation of 2-propanol with carbonyl(halogeno)phosphine-rhodium complexes
  作者：Kotohiro Nomura、Yasukazu Saito、Sumio Shinoda

  DOI：10.1016/0304-5102(89)80084-7

  日期：1989.6

  Photocatalytic dehydrogenation of 2-propanol, yielding acetone and dihydrogen, proceeded at high turnover frequencies with carbonyl(halogeno) phosphine-rhodium complexes RhX(CO)(PR3)2 (X = halogen and PR3 = t-phosphine) under excitation conditions for the metal-to-ligand charge transfer. The three-coordinate species RhX(PR3)2 generated by photodissociation of the CO ligand was responsible for the catalytic cycle

  在激发条件下，羰基（卤素）膦-铑配合物RhX（CO）（PR 3）2（X =卤素和PR 3 =叔膦）以高周转频率进行2-丙醇的光催化脱氢反应，生成丙酮和二氢。用于金属到配体的电荷转移。通过CO配体的光离解产生的三个配位物种RhX（PR 3）2导致了催化循环，而与配体的种类无关。电子和空间因素对膦配体的重要性都得到了证明。
• Direct oxidative addition–reductive elimination reactions between trans-[MCl(CO)L₂] and [MCl₃(CO)L₂] or trans-[PtCl₄(PEt₃)₂](M = Rh or Ir, L = tertiary phosphine)
  作者：Subhi Al-Jibori、Christopher Crocker、Bernard L. Shaw

  DOI：10.1039/dt9810000319

  日期：——

  Complexes of the type trans-[MCl(CO)L2] and [MCl3(CO)L2], M = Rh or Ir, L = PMe2Ph or PEt2Ph, have been shown to react with each other, presumably by a double chloro-bridged intermediate, and undergo rapid oxidative addition–reductive elimination; phosphine exchange is much slower. Similar results were obtained when trans-[PtCl4(PEt3)2] was treated with trans-[MCl(CO)(PEt3)2], M = Rh or Ir, for which

  该类型的复合物的反式- [的MC1（CO）L- 2 ]和[的MC1 3（CO）L- 2 ]，M =铑或铱，L = PME 2 pH或PET 2 PH，已显示出彼此反应，大概是由一个双氯桥联的中间体，并进行了快速的氧化加成-还原消除；膦的交换要慢得多。用反式-[MCl（CO）（PEt 3）2 ]，M = Rh或Ir处理反式-[PtCl 4（PEt 3）2 ]时，获得了相似的结果，可将其快速完全转化为反式-[PtCl 2（PEt3） 2 ]和[MCl 3（CO）（PEt 3） 2 ]发生。给出了磷31 nmr数据。
• Aresta, Michele; Tommasi, Immacolata; Quaranta, Eugenie, Inorganic Chemistry, 1996, vol. 35, # 14, p. 4254 - 4260
  作者：Aresta, Michele、Tommasi, Immacolata、Quaranta, Eugenie、Fragale, Carlo、Mascetti, Joelle、Tranquille, Michel、Galan, Florence、Fouassier, Monique

  DOI：——

  日期：——