RhCl(P(p-tolyl)3)3 | 24554-70-9

• 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: RhCl(P(p-tolyl)3)3
• 英文别名: {RhCl(P(C6H4Me-4)3)3}
• CAS: 24554-70-9
• 化学式: C₆₃H₆₃ClP₃Rh
• 分子量: 1051.47
• InChiKey: LXXLWISOCOEUSI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  13.8
• 重原子数：
  68.0
• 可旋转键数：
  12.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  RhCl(P(p-tolyl)3)3 在 H₂ 作用下， 以 甲苯 为溶剂， 生成 H2RhCl(P(4-tolyl)3)3
  参考文献：
  名称：

  方平面铑(I)化合物与氢反应的核磁共振和热力学研究

  摘要：

  已经研究了通式 (P(4-tolyl)/sub 3/)/sub 2/RhClB 的方形平面铑 (I) 配合物与 H/sub 2/ 的反应，其中 B 是 P(4-tolyl) /sub 3/、吡啶或四氢噻吩。NMR 研究证实，在所有情况下，产物几何结构都有两个相互顺式的氢和两个相互反式的膦。报道了吡啶从氢化物的解离速率，并与膦的解离速率进行了比较。报告了由膦和四氢噻吩加合物活化 H/sub 2/ 的热力学数据。根据这些信息，可以计算金属-氢键强度，并确定 B 对这个数量的影响。

  DOI：

  10.1021/ja00341a025
• 作为产物：
  描述：

  [(1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)Rh(P(p-tolyl)3)2Cl] 以 二氯甲烷 为溶剂， 生成 RhCl(P(p-tolyl)3)3
  参考文献：
  名称：

  Irreversible cleavage of a carbene–rhodium bond in Rh-N-heterocyclic carbene complexes: implications for catalysis

  摘要：

  Despite the generally accepted belief that carbene-metal bonds are strong and do not dissociate, the reaction of Rh-N-heterocyclic carbene complexes with triphenylphosphine in dichloroethane was determined to take place via cleavage of the Rh-carbene bond. The products of this reaction are Wilkinson's catalyst and a bisimiclazolium salt derived from reaction between dichloroethane and two equivalents of the carbene. The implications of this reaction for catalysis are significant since the carbene complex shows lower activity than Wilkinson's catalyst in hydrogenation reactions. In non-halogenated solvents, the catalyst shows higher stability, such that the rate of exchange with free phosphine could be measured, and was determined to be ca. 10 times slower than in Wilkinson's catalyst. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.07.021

文献信息

• Rhodium Complexes of 1,4-Disubstituted-1,2,3-butatrienes: Their Preparation and Reactivity
  作者：Noriyuki Suzuki、Yoshiyuki Fukuda、Chae Eun Kim、Hidemichi Takahara、Masakazu Iwasaki、Masahiko Saburi、Masayoshi Nishiura、Yasuo Wakatsuki

  DOI：10.1246/cl.2003.16

  日期：2003.1

  rhodium-(Z)-butatriene complexes 3. The butatrienes coordinated to Rh with the central double bond in an η2-fashion. (Z)-Butatrienes on 3 isomerized to (E)-form at 70 °C to afford (E)-butatriene complexes 4 with excellent E/Z ratios (E/Z = 97/3–99/1). The molecular structure of 4b (R = SiMe3, Ar = p-tolyl) was determined by X-ray diffraction analysis. Hydrosilation of 1 was catalyzed by rhodium complexes to give

  1,4-二取代丁三烯，(Z)-R-CH=C=C=CH-R (1, R = SiMe3, t-Bu)，与 RhCl(PAr3)3 (Ar = Ph, p-tolyl ) 得到铑-(Z)-丁三烯配合物 3. 丁三烯以 η2 方式与中心双键配位到 Rh。3 上的 (Z)-丁三烯在 70 °C 下异构化为 (E)-形式，以提供具有优异 E/Z 比 (E/Z = 97/3–99/1) 的 (E)-丁三烯配合物 4。4b (R = SiMe3, Ar = p-tolyl) 的分子结构通过 X 射线衍射分析确定。1 的氢化硅烷由铑配合物催化得到丙二烯作为主要产物，伴随着 1,3-二烯作为次要产物，这是硅烷的 2,1-加成和 2,3-反加成的结果。
• Different structural features of half-sandwich complexes of rhodium(<scp>I</scp>) containing the η⁵-1,2,4-triphosphacyclopentadienyl ring. Syntheses and³¹P n.m.r. spectra of [Rh(η⁵-C₂R₂P₃)LL′][R = Bu^t, L = L′= PPh₃,P(p-tolyl)₃; L = CO, L′= PPh₃; LL′= cyclo-octa-1,5-diene; R = adamantyl, L = PMe₃,PPh₃]; crystal and molecular structure of [Rh(η⁵-C₂Bu^t₂P₃)(η⁴-C₈H₁₂)]
  作者：Rainer Bartsch、Peter B. Hitchcock、Timothy J. Madden、Mohamed F. Meidine、John F. Nixon、Hongrui Wang

  DOI：10.1039/c39880001475

  日期：——

  First examples of η5-1,2,4-triphosphacyclopentadienyl complexes of rhodium are reported and their structures, elucidated by 31P n.m.r. spectroscopy and X-ray diffraction studies, show interesting differences.

  首次报道了铑的η5-1,2,4-三膦杂环戊二烯络合物的实例，其结构通过31P核磁共振光谱和X射线衍射研究得以阐明，显示出有趣的差异。
• Preparation and properties of tetrahedro-tetraphosphorus complexes of rhodium and iridium. Molecular and electronic structure of [RhCl(.eta.2-P4)(PPh3)2]
  作者：Alvin P. Ginsberg、W. Edward. Lindsell、Kevin J. McCullough、Charles R. Sprinkle、Alan J. Welch

  DOI：10.1021/ja00263a010

  日期：1986.2

  Rh(I) or Ir(I) complexes (MXL/sub 3/) (M = Rh, X = Cl, Br, I, L = PPh/sub 3/; M = Rh, X = Cl, L = P(p-tol)/sub 3/, P(m-tol)/sub 3/, AsPh/sub 3/; M = Ir, X = Cl, L = PPh/sub 3/) to form yellow or orange tetrahedro-tetraphosphorus complexes (MX(P/sub 4/)L/sub 2/). The complexes are characterized by /sup 31/P NMR, Raman, and infrared spectroscopies. An X-ray structure determination on (RhCl(P/sub 4/)(PPh/sub

  在 -78/sup 0/C 溶解在二氯甲烷或乙醚中的白磷与 Rh(I) 或 Ir(I) 配合物 (MXL/sub 3/) (M = Rh, X = Cl, Br, I, L = PPh/sub 3/; M = Rh, X = Cl, L = P(p-tol)/sub 3/, P(m-tol)/sub 3/, AsPh/sub 3/; M = Ir, X = Cl, L = PPh/sub 3/) 形成黄色或橙色四面体-四磷复合物 (MX(P/sub 4/)L/sub 2/)。配合物通过/sup 31/P NMR、拉曼和红外光谱表征。(RhCl(P/sub 4/)(PPh/sub 3/)/sub 2/) x 2CH/sub 2/Cl/sub 2/ 在 185 K 下的 X 射线结构测定显示晶体为三斜晶系，空间P1组，a = 11.853 (2) A, b = 12.568 (8) A, c =
• Rhodium−Hydrogen−Tin Three-Center Bonds. NMR (¹H, ³¹P, ¹⁰³Rh, ¹¹⁹Sn) Study of [Rh(Cl)(H)(SnPh₃)(PPh₃)(py)] and Related Compounds
  作者：Laurence Carlton

  DOI：10.1021/ic991054g

  日期：2000.10.1

  (f), Cl (g)) with Ph3SnH in solutions containing pyridines (4-Rpy; R = CO2Me, H, NMe2), 1-methylimidazole (1-Meim), and benzonitriles (4-RC6H4CN; R = COMe, H, NMe2) (L). NMR data for the series of complexes 2 in which ligands X, L, and, for X = Cl, the phosphine P(4-C6H4R)3 (R = F, H, Me) were varied independently show systematic changes in the parameters δ(119Sn), δ(103Rh), J(119Sn−1H), and J(103Rh−119Sn)

  配合物反式-[Rh(NCBPh3)(H)(SnPh3)(PPh3)2] (1) 在二氯甲烷中于 22 °C 与吡啶和取代的吡啶 (L) 反应生成 [Rh(NCBPh3)(H)(SnPh3 )(PPh3)(L)] (2a) 并在 -25 °C 下得到反式-[Rh(NCBPh3)(H)(SnPh3)(PPh3)2(L)] (3a)。这些配合物和许多类似物可以通过 [Rh(X)(PPh3)3] (X = NCBPh3 (a), N(CN)2 (b), NCS (c) 的反应制备（大部分仅在溶液中） , N3 (d), NCO (e), O2CCF3 (f), Cl (g)) 与 Ph3SnH 在含有吡啶 (4-Rpy; R = CO2Me, H, NMe2)、1-甲基咪唑 (1-Meim) 的溶液中，和苯甲腈 (4-RC6H4CN; R = COMe, H, NMe2) (L)。配合物 2 系列的
• Regioselectivity in the rhodium catalysed 1,4-hydrosilylation of isoprene. Aspects on reaction conditions and ligands
  作者：Magnus Gustafsson、Torbjörn Frejd

  DOI：10.1016/j.jorganchem.2003.09.054

  日期：2004.1

  affect the isomer distribution between tail-product (I) and head-product (II). The choice of ligands had the greater influence, where RhI-based catalysts with the strong electron withdrawing ligand CO favoured production of isomer II, while RhI catalysts with strong electron donating ligands (for example triarylphosphines) gave isomer I as the main product. In contrast to the square planar carbonyl complex

  研究了Rh催化异戊二烯的1，4-氢化硅烷化反应中的区域选择性。溶剂和温度的变化不会显着影响尾产物（I）和头产物（II）之间的异构体分布。配体的选择具有更大的影响力，其中具有强吸电子配体CO的Rh I基催化剂有利于异构体II的生产，而具有强给电子配体的Rh I催化剂（例如三芳基膦）以异构体I为主要产物。与方形平面羰基络合物RhCl（CO）（PPh 3）2相比，方形平面硫羰基络合物RhCl（CS）（PPh3）2，以I为主要异构体。