lithium [(dicyclohexylphosphino)ethyl]cyclopentadienide | 202843-37-6

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: lithium [(dicyclohexylphosphino)ethyl]cyclopentadienide
• 英文别名: Li[C5H4CH2CH2PCy2]；lithium;dicyclohexyl(2-cyclopenta-2,4-dien-1-ylethyl)phosphane
• CAS: 202843-37-6
• 化学式: C₁₉H₃₀P*Li
• 分子量: 296.362
• InChiKey: RYYVTHDYYFNWKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.74
• 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：

  三氯一茂钛 、 lithium [(dicyclohexylphosphino)ethyl]cyclopentadienide 以 四氢呋喃 为溶剂， 以80%的产率得到(η5-C5H5)(η5-C5H4(CH2)2P(cyclohexyl)2)TiCl2
  参考文献：
  名称：

  Ti–Ru bimetallic complexes: catalysts for ring-closing metathesis

  摘要：

  The reaction of the titanocene monophosphanes (1-4) with the dimer [(p-cymene)RuCl2](2) gives the heterobimetallic compounds (p-cymene)[(eta(5)-C5H5)(mu-eta(5):eta(1)-C5H4(CR2)(n)PR2')TiCl2]RuCl2 (5-8). The structure of 8, determined by X-ray diffraction, is reported here, A preliminary assessment of the performance of these complexes in ring-closing metathesis (RCM) revealed an excellent Ti-Ru-allenylidene pre-catalyst 12. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01248-7
• 作为产物：
  描述：

  二环己基磷化锂 、 螺[2.4]庚-4,6-二烯 以 四氢呋喃 为溶剂， 反应 12.0h， 以56%的产率得到lithium [(dicyclohexylphosphino)ethyl]cyclopentadienide
  参考文献：
  名称：

  Phosphane coordination to rare earth metal centers: monomeric, solvent-free complexes of type Cp′2LnX with phosphanoethyl substituted cyclopentadienyl ligands

  摘要：

  The reaction of phosphanoethyl substituted cyclopentadienides [C5H4CH2CH2PR2]M, R = Me, Cy, t-Bu, Ph, M = Li, K with LnX(3) (Ln = rare earth metal, X=Cl-, CF3SO3-) afforded twofold substituted metal complexes of the type (C5H4CH2CH2PR2](2)LnX. Using the dianionic ligand Li-2[(C5H4CH2CH2)(2)PMe] phosphano bridged ansa metallocene derivatives [(C5H4CH2CH2)(2)PMe]LnX( (Ln = Y, Lu; X = Cl-, CF3SO3-) were isolated. The complexes are soluble in toluene, monomeric and free of solvent. According to X-ray studies on [C5H4CH2CH2PMe2](2)YCl, a distorted trigonal bipyramid with two axial phosphano groups and two equatorial cyclopentadienyl moieties is the structural motif, the third equatorial site being occupied by the halide ligand. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00205-9

文献信息

• Donor-Ligand-Substituted Cyclopentadienylchromium(III) Complexes:  A New Class of Alkene Polymerization Catalyst. 2. Phosphinoalkyl-Substituted Systems
  作者：Arno Döhring、Vidar R. Jensen、Peter W. Jolly、Walter Thiel、Jan C. Weber

  DOI：10.1021/om010146m

  日期：2001.5.1

  A series of phosphinoalkyl-substituted cyclopentadienylchromium complexes, e.g., (η1:η5-R2PC2H4C5H4)CrCl2, have been synthesized. The complexation of the P atom to the chromium has been confirmed by crystal structure determinations. Activated by methylalumoxane (MAO), these compounds catalyze the oligomerization and polymerization of ethylene. The catalytic activity and the degree of oligomerization

  一系列phosphinoalkyl取代cyclopentadienylchromium复合物，例如，（η 1：η 5 -R 2 PC 2 ħ 4 ç 5 ħ 4）的CrCl 2，已经合成。通过晶体结构测定已经证实了P原子与铬的络合。这些化合物被甲基铝氧烷（MAO）活化，催化乙烯的低聚和聚合。催化活性和低聚度受供体原子上取代基的空间特性控制：取代基越小，活性越高，低聚物的分子量越低。密度泛函计算表明，通过β-氢转移的传播和终止对于小的取代基而言是竞争性的，并且后者的过程（涉及自旋反转）随着取代基尺寸的增加而变得选择性不利。
• Solvent-free ketone hydrogenations catalyzed by molybdenum complexesElectronic supplementary information (ESI) available: additional spectroscopic data and description of the synthetic procedures. See http://www.rsc.org/suppdata/cc/b4/b401760a/
  作者：Barbara F. M. Kimmich、Paul J. Fagan、Elisabeth Hauptman、R. Morris Bullock

  DOI：10.1039/b401760a

  日期：——

  Et2CO is hydrogenated under solvent-free conditions using a catalyst prepared by hydride abstraction from HMo(CO)2[η5:η1-C5H4(CH2)2PCy2]; the catalyst functions at low catalyst loadings (<0.4 mol%).

  Et2CO在无溶剂条件下使用从HMo(CO)2[η5:η1-C5H4(CH2)2PCy2]抽氢化物制备的催化剂进行氢化；该催化剂在低催化剂负载量（<0.4 mol%）下发挥作用。
• Molybdenum Carbonyl Complexes in the Solvent-Free Catalytic Hydrogenation of Ketones
  作者：Barbara F. M. Kimmich、Paul J. Fagan、Elisabeth Hauptman、William J. Marshall、R. Morris Bullock

  DOI：10.1021/om050564h

  日期：2005.12.1

  The heterodifunctional ligand Li[eta(5)-C5H4(CH2)(2)PR2] (R = Ph, Cy, and Bu-t) reacts with MO(CO)(3)(diglyme) to give the molybdenum anion complex LiMo(CO)(3) [eta(5)-C5H4(CH2)(2)PR2]}. Protonation with HOAc gives the metal hydride complexes HMo(CO)(2)[eta(5):eta(1)-C5H4(CH2)(2)PR2], in which the phosphine and cyclopentadienyl ligands are linked by a two-carbon bridge. Crystal structures of HMo(CO)(2) [eta(5):eta(1)-C5H4(CH2)(2)PR2] with all three R groups (R = Ph, Cy, and tBu) are reported. Syntheses of the C-3-bridged complex, HMo(CO)(2) [eta(5):eta(1)-C4H5(CH2)(3)-PPh2], and a W analogue, HW(CO)(3) [eta(5)-C5H4(CH2)(2)(PBu2)-Bu-t], were carried out by analogous routes. Hydride transfer to Ph3C+BAr'(-)(4) [Ar' = 3,5-bis(trifluoromethyl)phenyl] from the catalyst precursors HMo(CO)(2) [eta(5):eta(1)-C5H4(CH2)(2)PR2] leads to homogeneous catalysts for hydrogenation of ketones, with the best performance being found for R = Cy. Protonation of HMo(CO)(2)[eta(5):eta(1)-C5H4(CH2)(2)PR2], by HOTf leads to metal triflate complexes (TfO)MO(CO)(2)[eta(5):eta(1)-C5H4(CH2)(2)PR2], which are used in ketone hydrogenation. Compared to the previously prepared complexes that did not have the phosphine and Cp linked together, these new complexes provide catalysts that have much longer lifetimes (up to about 500 turnovers) and higher thermal stability. Solvent-free ketone hydrogenation can be carried out with these complexes at catalyst loadings as low as 0.1 mol %.
• Ruthenium titanocene and ruthenium titanium half-sandwich bimetallic complexes in catalytic cyclopropanation
  作者：Jérôme Goux、Pierre Le Gendre、Philippe Richard、Claude Moïse

  DOI：10.1016/j.jorganchem.2004.09.021

  日期：2005.1

  The reaction of the phosphine functionalised titanium half-sandwich complexes 7, 9 and 10 with the binuclear complex [(p-cymene)RuCl2](2) allowed the access to three new early-late bimetallic complexes (p-cymene)[(mu-eta(5):eta(1)-C5H4(CH2)(n)PR2)TiX3]RuCl2(11-13). The structure of 11 (n = 0, X = Cl) has been confirmed by X-ray diffraction. The ruthenium titanium half-sandwich bimetallic complexes so formed and the ruthenium titanocene analogues 4-6 catalyse the addition of ethyl diazoacetate to styrene with high selectivity toward cyclopropanation versus metathesis contrary to the monometallic complexes (p-cymene)RuCl2PR3. (C) 2004 Elsevier B.V. All rights reserved.
• Bimetallic complexes with ruthenium and tantalocene moieties: Synthesis and use in a catalytic cyclopropanation reaction
  作者：Jérôme Goux、Pierre Le Gendre、Philippe Richard、Claude Moïse

  DOI：10.1016/j.jorganchem.2006.03.029

  日期：2006.7

  The reaction of the tantalocene dichloride monophosphines (1-2) with the binuclear complex [(p-cymene)RuCl2](2) gives the heterobimetallic compounds (p-cymene)[(eta(5)-C5H5)(mu-eta(5):eta(1)-C5H4(CH2)(2)PR2)TaCl2]RuCl2 (3-4). The air oxidation of these bimetallic species 3-4, leads to the cationic hydroxo tantalum ruthenium derivatives 5-6. The last ones are easily deprotonated by a base to afford the oxo analogues 7-8. A preliminary assessment in catalytic cyclopropanation of styrene with tantalum ruthenium bimetallic complexes 3-8 as precatalysts revealed a cooperative effect with a subtle role of the early metal fragment. (c) 2006 Elsevier B.V. All rights reserved.