cis,trans,cis-[Rh(H)2(PPh3)2(acetone)2]PF6 | 82404-88-4

• 英文名称: cis,trans,cis-[Rh(H)2(PPh3)2(acetone)2]PF6
• 英文别名: {Rh(H)2(acetone)2(triphenylphosphine)2}PF6；[Rh(III)(acetone)2(H)2(PPh3)2]PF6
• CAS: 82404-88-4；79027-52-4
• 化学式: C₄₂H₄₄O₂P₂Rh*F₆P
• 分子量: 890.627
• InChiKey: ZPJXRMAJOCBMMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  cis,trans,cis-[Rh(H)2(PPh3)2(acetone)2]PF6 、 2 2'-联嘧啶 以 二氯甲烷 为溶剂， 以73%的产率得到{Rh(H)2(2,2'-bipyrimidine)(triphenylphosphine)2}PF6*0.5CH2Cl2
  参考文献：
  名称：

  Rhodium(III) cis-dihydrido complexes with 3,6-bis(2′-pyridyl)pyridazine (dppn) and bidiazines. Crystal and molecular structure of [Rh(H)2(dppn)(PPh3)2]PF6· CH2Cl2

  摘要：

  DOI：

  10.1016/s0020-1693(00)83379-4
• 作为产物：
  描述：

  氢气 、 丙酮 、 (1,5-环辛二烯)二(三苯基膦)六氟磷酸铑二氯甲烷络合物(1:1) 以 丙酮 为溶剂， 生成 cis,trans,cis-[Rh(H)2(PPh3)2(acetone)2]PF6
  参考文献：
  名称：

  Rh（III）-二氢-双（膦）配合物与氨基脲的相互作用。

  摘要：

  顺式，反式，顺式-[Rh（H）2（PR3）2（丙酮）2] PF6配合物（R =芳基或R3 = Ph2Me，Ph2Et）在H2下与E-半咔唑酮相互作用得到Rh（III）-二氢-双（膦）-半脲类顺式，反式-[Rh（H）2（PR3）2 {R'（R''）C = NN（H）CONH2}] PF6，其中R'和R''为Ph ，等等或我。通常通过元素分析，31P {1H} NMR，1H NMR和IR光谱以及MS来表征配合物。三种PPh3配合物的X射线分析表明，亚氨基-N原子和羰基-O原子螯合了E-半咔唑酮。相比之下，[Rh（H）2（PPhMe2）2（丙酮）2] PF6与苯乙酮半卡巴gives的相应反应可得到原金属化的半卡巴zone物种顺式-[RhH（PPhMe2）2 {o-C6H4（Me）C = NN（H）CONH2}] PF6。还报道了E-苯乙酮半卡巴zone的X射线结构。铑催化的

  DOI：

  10.1021/ic0489185

文献信息

• Rates and activation parameters for solvent exchange with [M(PR3)2-(solvent)2H2]+(M = Rh III or Ir III , R = cyclohexyl or phenyl) cations
  作者：Oliver W. Howarth、Colin H. McAteer、Peter Moore、George E. Morris

  DOI：10.1039/dt9810001481

  日期：——

  and, where possible, stopped-flow Fourier-transform n.m.r., rates and activation parameters have been determined for solvent exchange with complexes of the type [M(PR3)2(solvent)2H2]+(M = RhIII or IrIII; R = phenyl, solvent = MeCN or Me2CO; R = cyclohexyl, solvent = MeCN) in [2H2]-dichloromethane solution. In all cases the co-ordinated solvent molecules are in trans positions with respect to the hydride

  使用1 H nmr线扩大，并在可能的情况下使用停流傅立叶变换nmr，确定了与[M（PR 3）2（溶剂）2 H 2 ] +型配合物进行溶剂交换的速率和活化参数（M ＝ Rh III或Ir III； R ＝苯基，溶剂＝ MeCN或Me 2 CO； R ＝环己基，溶剂＝ MeCN）在[ 2 H 2 ]-二氯甲烷溶液中。在所有情况下，配位的溶剂分子都相对于氢化物配体处于反位，并且在298 K时，各种络合物具有用于溶剂交换的速率常数（k 1）相差几乎10 7 ; k 1（Rh）> k 1（lr）是因为对于类似物种ΔH ‡（Rh）< ΔH ‡（lr），并且丙酮溶剂化物比乙腈配合物更不稳定，因为ΔH ‡值较低。ΔS ‡的值显着为正（当M = Rh III时为8–32 JK –1 mol –1，当M = Ir III时为25–30 JK –1 mol –1），与解离度D一致机制。[M（PR 3）2（溶剂）2
• Synthesis, reactions, and crystal structures of carbonyl-free hydride-bridged mixed organotransition metal derivatives of bis(phosphine)-rhodium(<scp>III</scp>) or -iridium(<scp>III</scp>) cations with dihydridobis(η⁵-cyclopentadienyl)-molybdenum and tungsten
  作者：Oliver W. Howarth、Colin H. McAteer、Peter Moore、George E. Morris、Nathaniel W. Alcock

  DOI：10.1039/dt9820000541

  日期：——

  The Lewis bases [MH2(η5-C5H5)2](M = MO or W) displace acetone from the labile complex [RhH2(PPh3)2(OCMe2)2][PF6] to give [(PPh3)2Rh(µ-H)2M(η5-C5H5)2][PF6] which are readily cleaved by pyridine or HCl and undergo H/D exchange at the cyclopentadienyl rings under mild conditions. The tungsten product (3b) is monoclinic, space group P21/c, a= 12.511(1), b= 9.273(1), c= 36.036(6)Å, β= 98.98(1)°, and Z=

  路易斯碱[MH 2（η 5 -C 5 H ^ 5）2 ]（M = Mo或W）从不稳定的复杂位移丙酮[RhH的2（PPH 3）2（OCME 2）2 ] [PF 6 ]，得到[（PPH 3）2的Rh（μ-H）2 M（η 5 -C 5 H ^ 5）2 ] [PF 6 ]，其容易由吡啶或HCl裂解并经历H /在环戊二烯基环的温和条件下d交换。钨产品（3b）是单斜晶系，空间群P2 1 / ç，一个= 12.511（1），b = 9.273（1），C ^ = 36.036（6）α，β= 98.98（1）°，ž具有= 4.6 052观察到的反射升/σ（升）3.0细化为R = 0.039。金属原子通过两个桥连的H原子连接，并且具有Rh-W = 2.7206（7）Å。钨原子具有正常W（η 5 -C 5 H ^ 5）2的几何形状（二面角136°）和铑原子具有正方形平面协调。的反应[MH 2（η 5 -C 5 H
• Rhodium(III)-Cyclometalated-Imine Complexes:  Solution Behavior and Reactivity with Molecular Hydrogen
  作者：Paolo Marcazzan、Brian O. Patrick、Brian R. James

  DOI：10.1021/om049121o

  日期：2005.3.1

  Acetone solutions of cis, trans, cis-[Rh(H)(2)(PPh3)(2)(acetone)(2)] PF6 and cis-[Rh(PPh3)(2)(acetone)(2)]PF6 react with the imines RN=CR '(R ''), where R = PhCH2, Ph, or C6H11; R '= H or Me; and R '' = Ph or P-OMe-C6H4, to form orthometalated complexes exemplified by [Rh(H)RN= CR '(o-C6H4)}(PPh3)(2)(acetone)]PF6 that are generally characterized spectroscopically, and in one case (where R = PhCH2, R ' = Me, and R '' = p-OMe-C6H4) by X-ray crystallography. These complexes maintain their integrity in acetone solution and show no reaction toward 1 atm H-2 at ambient conditions. In MeOH, the complexes in which R ' = Me simply change to the corresponding MeOH derivative, but when R ' = H they are partially converted to the non-orthometalated, eta(1)-N-imine species [Rh(PPh3)(2)(RN=CHR '')(MeOH)]PF6 (I), and in MeOH, stoichiometric hydrogenation of the imine to the corresponding amine occurs via I. We have shown recently (Inorg. Chem. 2004, 43, 4820) that the catalyzed hydrogenation of PhCH2N=C(H)Ph to dibenzylamine using cis, trans, cis- [Rh(H)(2)(PPh3)(2)(MeOH)(2)] PF6 as catalyst precursor in MeOH proceeds via a cationic Rh-(eta(1)-N-imine)(amine) intermediate (II), analogous to I but with the MeOH replaced by the amine that is formed via hydrolysis of the imine by the presence of adventitious water. Intermediate I (R = PhCH2, R '' = Ph) is shown to be somewhat less active than II toward H-2, but both intermediates provide viable pathways for hydrogenation of the imine. The orthometalated imine-amine complex [Rh(H)PhCH2N=C(Me)(o-C6H4)}(PPh3)(2)(NH2CH2Ph)]PF6, where the benzylamine comes from imine hydrolysis, is also isolated and characterized crystallographically.
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Rh: SVol.B3, 4.24.13.3, page 152 - 153
  作者：

  DOI：——

  日期：——