trans-[Rh(CO)Cl(ethyldiphenylphosphine)2] | 14875-00-4

• 英文名称: trans-[Rh(CO)Cl(ethyldiphenylphosphine)2]
• 英文别名: trans-{(Ph2PEt)Rh(CO)Cl}
• CAS: 14875-00-4；15663-57-7
• 化学式: C₂₉H₃₀ClOP₂Rh
• 分子量: 594.863
• InChiKey: CKJZPOXVOXGNHU-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：

  trans-[Rh(CO)Cl(ethyldiphenylphosphine)2] 以 not given 为溶剂， 生成 bis(ethyldiphenyl-l5-phosphaneyl)rhodium(III) chloride
  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：

  RhCl((13)CO)(PEtPh2)2 在 一氧化碳 作用下， 以 not given 为溶剂， 生成 trans-[Rh(CO)Cl(ethyldiphenylphosphine)2]
  参考文献：
  名称：

  羰基（卤代）膦-铑配合物对2-丙醇的光催化脱氢

  摘要：

  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。

  DOI：

  10.1016/0304-5102(89)80084-7

文献信息

• Phosphinerhodium complexes as homogeneous catalysts
  作者：László Kollár、Szilárd Tōrōs、Bálint Heil、László Markó

  DOI：10.1016/s0022-328x(00)94429-2

  日期：1980.6

  In the hydrogenation of olefins in alcoholic solvents catalysed by phosphinerhodium complexes a hydrogen transfer reaction from the alcohols to the olefins takes place alongside the main reaction. With primary alcohols the aldehydes formed are decarbonylated and the in situ catalysts formed from [Rh(diene)Cl]2 and phosphines are partially converted into Rh(CO)(PR3)2Cl type complexes and thereby deactivated

  在由次膦酸酯配合物催化的醇溶剂中烯烃的氢化中，与主要反应同时发生了从醇到烯烃的氢转移反应。用伯醇将形成的醛脱羰，并将由[Rh（二烯）Cl] 2和膦形成的原位催化剂部分转化为Rh（CO）（PR 3）2 Cl型络合物，从而使其失活。
• 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
• Reactions of di-µ-chloro-bis[cyclo-octa-1,5-dienerhodium(<scp>I</scp>)] with carbon mono-oxide and mono-, di-, or tri-tertiary phosphines, or 1,2-bis(diphenylarsino) ethane
  作者：Alan R. Sanger

  DOI：10.1039/dt9770000120

  日期：——

  Reactions of [Rh2(cod)2Cl2](cod = cyclo-octa-1,5-diene) with CO and PXPh2(X = Et or Cl), Ph2P[CH2]nPPh2(n= 1–4), 4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxoiane (bdmo), cis-Ph2PCH:CHPPh2, Ph2As[CH2]2AsPh2, (Ph2PCH2)3CMe, or P(CH2CH2PPh2)2Ph, give trans-[Rh(CO)Cl(PXPh2)2], [Rh(CO)Cl(Ph2P[CH2]nPPh2)}m](m= 1, n= 2; m= 2, n= 1, 3, or 4). or related complexes. Under different conditions, a

  [Rh 2（cod）2 Cl 2 ]（cod =环辛-1,5-二烯）与CO和PXPh 2（X = Et或Cl），Ph 2 P [CH 2 ] n PPh 2（n = 1-4），4,5-双（二苯基膦甲基）-2,2-二甲基-1,3-二氧杂戊环（bdmo），顺式-Ph 2 PCH：CHPPh 2，Ph 2 As [CH 2 ] 2 AsPh 2， （Ph 2 PCH 2）3 CMe或P（CH 2 CH 2 PPh 2）2Ph，给出反式-[Rh（CO）Cl（PXPh 2）2 ]，[Rh（CO）Cl（Ph 2 P [CH 2 ] n PPh 2）} m ]（m = 1，n = 2; m = 2，n = 1、3或4）。或相关的综合体。在不同条件下，获得了Ph 2 P [CH 2 ] 2 PPh 2与配位二烯的配合物。Ph 2 P [CH 2 ] n PPh 2的过量会产生[Rh（Ph 2 P [CH
• Preparation and reactivity of iodomethyl complexes of rhodium(III); crystal and molecular structure of carbonylchloroiodo(iodomethyl)bis(triethylphosphine)rhodium(III)
  作者：Rosslyn C. Gash、David J. Cole-Hamilton、Robin Whyman、John C. Barnes、Michael C. Simpson

  DOI：10.1039/dt9940001963

  日期：——

  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.
• Sanger, Alan R., Canadian Journal of Chemistry, 1984, vol. 62, p. 822 - 825
  作者：Sanger, Alan R.

  DOI：——

  日期：——