phenoxytris(triphenyl-l5-phosphaneyl)rhodium | 21276-23-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: phenoxytris(triphenyl-l5-phosphaneyl)rhodium
• 英文别名: Rh(OPh)(PPh3)3
• CAS: 21276-23-3
• 化学式: C₆₀H₅₀OP₃Rh
• 分子量: 982.883
• InChiKey: URPYBQIJMKQFAL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.86
• 重原子数：
  65.0
• 可旋转键数：
  14.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  phenoxytris(triphenyl-l5-phosphaneyl)rhodium 以 正己烷 为溶剂， 生成
  参考文献：
  名称：

  包含金属-碳键的新的σ键结合的铑（I）配合物。一世

  摘要：

  报道了新的铑（I）配合物（Ph 3 P）3 RhR（R = Me，Ph）的合成。化合物与苯酚反应生成新的苯氧基衍生物（Ph 3 P）n RhOPh（n = 2,3）。基于NMR证据，提出了（Ph 3 P）3 RhMe的四面体或三角锥结构。加热后，后者失去了甲烷，可以证明提取的氢来自配体Ph 3 P的一个苯环的邻位，从而形成络合物（Ph 3 P）2（Ph 2 PC 6 H 4）Rh，其特征在于化学和物理手段。

  DOI：

  10.1016/s0022-328x(00)92654-8
• 作为产物：
  描述：

  Wilkinson's catalyst 、 sodium phenoxide 以 四氢呋喃 为溶剂， 以91%的产率得到phenoxytris(triphenyl-l5-phosphaneyl)rhodium
  参考文献：
  名称：

  Preparation, structure and properties of triphenylphosphine rhodium aryloxides

  摘要：

  The reaction of Wilkinson's catalyst with NaOAr in toluene cleanly affords the corresponding aryloxide complexes Rh(PPh3)(3)OAr (1), In solution, 1. exists in equilibrium with PPh3 and the corresponding Rh(PPh3)(2)(pi-ArO) (2). The addition of HOAr shifts the equilibrium completely toward the corresponding adducts 2.2HOAr, due to hydrogen bonding between the oxygen atom of the pi-coordinated OAr ligand and two molecules of HOAr. Heating of 1a-d in toluene at 60-80 degrees C leads to the elimination ui HOAr with concomitant cyclometallation uf a phenyl ring of one PPh3 ligand, affording mixtures of 1, 2.2HOAr, a cyclometallated Rh complex and PPh3. At room temperature, a reverse reaction slowly occurs to give equilibrium mixtures of 1, 2 and PPh3. Complexes 1 readily react with water, CO and H-2, affording Rh-2(PPh3)(4)( mu-OH)(2),Rh(PPh3)(2)(CO)OAr (3) and HRh(PPh3)(3), respectively. The latter complex was also obtained when complexes 1 were treated with methanol. The structures of the phenoxide complexes 1 and 2.2PhOH and of p-nitrophenoxide complex 3 were established by X-ray diffraction. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(98)00171-6

文献信息

• REGIOSELECTIVE C–O BOND CLEAVAGE OF ALLYLIC PHENYL CARBONATES PROMOTED BY GROUP 8 TRANSITION METAL HYDRIDO COMPLEXES
  作者：Yoshinori Hayashi、Sanshiro Komiya、Takakazu Yamamoto、Akio Yamamoto

  DOI：10.1246/cl.1984.977

  日期：1984.6.5

  Carbon–oxygen bonds in allylic phenyl carbonates are selectively cleaved by hydrido complexes of Co, Ru and Rh to give Co(OPh)L3, RuH(OPh)L2 and Rh(OPh)L3 with liberation of propylene and CO2. An intermediate complex RuH(O2COEt)L3 has been isolated in the reaction of RuH2(PPh3)4 with allyl ethyl carbonate. Reaction mechanisms are also discussed.

  Co、Ru 和 Rh 的氢化物配合物能选择性地断裂苄基苯基碳酸酯中的碳-氧键，生成 Co(OPh)L3、RuH(OPh)L2 和 Rh(OPh)L3，同时释放出丙烯和二氧化碳。在 RuH2(PPh3)4 与碳酸烯丙基乙酯的反应中，分离出了一种中间体配合物 RuH(O2COEt)L3。同时，本文还讨论了反应机理。
• π-Arene and π-phenoxo complexes of ruthenium and rhodium
  作者：David J. Cole-Hamilton、Robert J. Young、Geoffrey Wilkinson

  DOI：10.1039/dt9760001995

  日期：——

  of fluoroboric acid on dihydridotetrakis(triphenylphosphine)ruthenium(II) or on acetatohydridotris(tri-phenylphosphine) ruthenium(II) in methanol produces the salt [RuH(η6-C6H5PPh2)(PPh2)3][BF4] in which the phenyl group of one triphenylphosphine molecule is π-bonded to the metal. In the presence of benzene or toluene, similar arene complexes, [RuH(η6-Ar)(PPh3)2][BF4] are obtained.

  氟硼酸对二氢化作用（三苯基膦）合钌（II）或在acetatohydridotris（三苯基膦）合钌（II）在甲醇生产的盐[期RuH（η 6 -C 6 H ^ 5 PPH 2）（PPH 2）3 ] [BF 4 ]，其中一个三苯基膦分子的苯基与金属π键合。在苯或甲苯，类似芳烃络合物的存在下[期RuH（η 6 -Ar）（PPH 3）2 ] [BF 4 ]获得。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Rh: SVol.B3, 4.24.3.2, page 135 - 138
  作者：

  DOI：——

  日期：——
• Tris(triphenylphosphine)rhodium(I) complexes
  作者：W. Keim

  DOI：10.1016/s0022-328x(00)83654-2

  日期：1967.6
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Rh: SVol.B3, 4.24.6, page 139 - 140
  作者：

  DOI：——

  日期：——