lithium diphenylphosphinocyclopentadienyl | 83272-80-4

• 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: lithium diphenylphosphinocyclopentadienyl
• 英文别名: [(diphenylphosphino)cyclopentadienyl]lithium；lithium (diphenylphosphino)cyclopentadienide；lithium diphenylphosphino cyclopentadienide；lithium diphenylphosphinocyclopentadienide；lithium diphenylphosphanylcyclopentadiene
• CAS: 83272-80-4
• 化学式: C₁₇H₁₄LiP
• 分子量: 256.213
• InChiKey: GQKCBGNBRBYKPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  lithium diphenylphosphinocyclopentadienyl 、 tricarbonyl-tris(acetonitrile)tungsten(0) 以 甲苯 为溶剂， 以97%的产率得到Li(1+)*[(η5-C5H4PPh2)W(CO)3](1-)
  参考文献：
  名称：

  官能化的环戊二烯基配体的过渡金属衍生物。十六。的合成桥配合物[（μ-η 5 -C 5 H ^ 4 PPH 2）M（CO）2 ] 2（M =铬，钼，W）。的二氢化衍生物的X射线晶体结构[（μ-η 5 -C 5 H ^ 4 PPH 2）W（CO）2 H] 2

  摘要：

  Four synthetical methods, implying basically the oxidation of the anionic species [(eta(5)-C5H4PPh2)M(CO)(3)](-) [M = Cr, (2a(-)), Mo (2b(-)), W (2c(-))] to produce the new homobimetallic derivatives [(mu,eta(5)-C5H4PPh2)M(CO)(2)](2) (M-M), [M = Cr (1a), Mo (1b), W (1c)] of the heterodifunctional diphenylphosphinocyclopentadienyl bridging ligand, have been investigated. The first approach proceeds in two steps: thus the electrochemical oxidation of the complexes 2a(-) and 2b(-) leads to the metal-metal bonded dimetallic complexes [(eta(5)-C5H4PPh2)M(CO)(3)](2) (M-M), [M = Cr (5a), Mo (5b)]; the irradiation of these complexes 5a and 5b with a high-pressure Hg lamp affords the corresponding decarbonylated bridged complexes 1a and 1b. The second method, using silver tetrafluoroborate as the oxidant of the anions 2a(-) to 2c(-), leads to the formation of tetrametallic cyclic complexes of silver and Group 6 transition metals [(mu-eta(5)-C5H4PPh2[M(CO)(3)Ag](2), [M = Cr (6a), Mo (6b), W (6c)] but the splitting of these compounds into bimetallic complexes 1a-c and metallic silver appears neither easy nor selective. As a third procedure, the hydride complexes (eta(5)-C5H4PPh2)M(CO)(3)H [M = Cr (3a), Mo (3b), W (3c)] are irradiated with a high-pressure Hg lamp. This procedure is useful to prepare Ib but is non-selective in the two other cases, affording mainly bimetallic dihydrido-bridged complexes [(mu-eta(5)-C5H4PPh2)M(CO)(2)H](2) [M = Mo (7b), W (7c)] and 1a or 1b, as a result of the expected competition between the dehydrogenation and the decarbonylation processes. The X-ray molecular structure of 7c points out the transoid disposition of the hydride ligands, which could well be a factor of its inertness in a spontaneous dehydrogenation process towards 1c. Finally, the most efficient method requires the preliminary preparation of the iodo complexes (eta(5)-C5H4PPh2)M(CO)(3)I [M = Cr (4a), Mo (4b), W (4c)], which are reacted in toluene with their anionic parents 2(-). This last method is particularly useful for preparing 1a and 1c.

  DOI：

  10.1039/a706746a

文献信息

• Metalloligands containing samarium(III). Access to binuclear f-metal (samarium)-d-metal (rhodium) complexes
  作者：M. Visseaux、A. Dormond、M.M. Kubicki、C. Moïse、D. Baudry、M. Ephritikhine

  DOI：10.1016/0022-328x(92)80132-h

  日期：1992.7

  tetrahydrofuran). The X-ray crystal structure of (COT)Sm(C5H4PPh2(THF)2 is described. These metallophosphines reacted quantitatively with (C5H5)Rh(CO)2 to give phosphido-bridged bimetallic samarium(III)-rhodium(I) complexes (COT)Sm(μ-C5R4PR′2)Rh(C5H5)(CO) (R = H or Me; R′= Me or Ph). Crystal data: C33H38O2PSm, triclinic, Pa = 8.606(2), b = 11.458(3), c = 14.632(2) Å, α = 87.09(2), β = 86.93(2), γ = 87.18(2)°

  据报道，合成了新的二甲基膦基四甲基环戊二烯HC 5 Me 4 PMe 2及其钾盐KC 5 Me 4 PMe 2。该钾盐（以及已知的LiC 5 H 4 PPh 2和KC 5 Me 4 PPh 2）与[（COT）SMCl（THF）2 ] 2的反应产生了一系列金属配体（COT）Sm（C 5 [R 4 PR' 2（THF）ñ（R = H或Me; R'= Me或Ph值; ñ = 0或2; COT =η8-环辛酸酯基; THF ＝四氢呋喃）。描述了（COT）Sm（C 5 H 4 PPh 2（THF）2）的X射线晶体结构，这些金属膦与（C 5 H 5）Rh（CO）2进行了定量反应，生成了磷桥联双金属（（III） ） -铑（I）配合物（COT）的Sm（μ-C 5 - [R 4 PR' 2）的Rh（C 5 H ^ 5。）（CO）（R = H或Me; R'= Me或PH）晶体数据： C 33 H 38 O 2
• General Route to Dissymmetric Heteroannular-Functionalized Ferrocenyl 1,2-Diphosphines:  Selective Synthesis and Characterization of a New Class of Tri- and Tetrasubstituted Ferrocenyl Compounds
  作者：V. V. Ivanov、J.-C. Hierso、R. Amardeil、P. Meunier

  DOI：10.1021/om050882g

  日期：2006.2.1

  Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferrocenylphosphines (A-Fe-B). The proposed synthetic method represents a unique means to produce achiral dissymmetric 1,1‘,2-substituted ferrocenes (A-Fe-B) bearing a heteroannular 1‘-substituent which is different

  几个单取代的环戊二烯基阴离子（A- Li）和[1,2-双（二苯基膦基）-4-叔丁基环戊二烯基]锂（B - Li）与FeCl 2反应，得到一类新型的多齿二茂铁基膦（A -Fe- B）。拟议的合成方法代表了一种独特的方法，可生产非均相的1,1'，2-取代的二茂铁（A -Fe- B），其带有不同于同环1和2取代基的异环1'-取代基。两步反应的选择性有利于形成所需的不对称产物（A -Fe- B），而不是同时形成对称的二取代和四取代的二茂铁（A -Fe- A和B -Fe- B）。因此，该方法允许访问大量不对称的多齿金属配体，尤其是当人们认为功能化的Cp盐在数量和多样性方面不断扩展时。在此，重点放在金属配体的1 H，13 C和31 P NMR表征上。有几个例子显示出有趣的构象特性和罕见的“贯穿空间”磷核自旋耦合。
• The synthesis of dinuclear molybdenum ad tungsten complexes with the bridging heterodifunctional ligand C5H4PPh2: X-ray crystal structure of Mo2(μ-C5H4PPh2) (η5-C5 H5)(CO)5
  作者：Timothy J. Duckworth、Martin J. Mays、Gráinne Conole、Mary McPartlin

  DOI：10.1016/0022-328x(92)85097-g

  日期：1992.11

  the di-bridged complex Mo2(μ-C5H4PPh2)2(CO)4 (3). The molecular structure of MO2(μ-C5H4PPh2(η5-C5H5)(CO)5 (1a) has been determined by X-ray diffraction. Treatment of 1a, 1b and 3 with HBF4 gives the corresponding monoprotonated derivatives 4a, 4b and 5, respectively, in which the proton occupies a bridging site between the metal centres. The new mononuclear complexes Mo(η5-C5H4PPh2) (CO)3I (6) and M

  报道了由异双官能配体C 5 H 4 PPh 2桥接的钼和钨双核金属-金属键合配合物的合成和一些反应。新的配合物矩（μ-C 5 H ^ 4 PPH 2）（η 5 -C 5 H ^ 5）（CO）5 [M =钼（1A）; M = W（1B）〕，以及MO 2（μ-C 5 H ^ 4 PPH 2）（η 5 -C 5 H ^ 4 -PPh 2（CO）5（1C）已被表征，与膦取代的衍生物MOM-（μ-C一起5 ħ 4 PPH 2）（η 5 -C 5 H ^ 5）（CO）4 L [M =钼，L = PPH 2我（图2a） ; M = MO，L = P（OMe）3（2b）；M = W，L = PPH 2我（2C）]和二-桥连络合物的MO 2（μ-C 5 H ^ 4 PPH 2）2（CO）4（3）。MO的分子结构2（μ-C 5ħ 4 PPH 2（η 5 -C 5 H ^ 5）（CO）5（1A）已经由X射线衍射测定。用HBF
• Functionally substituted derivatives of (η5-cyclopentadienyl)triisopropoxytitanium and (η5-cyclopentadienyl)trichlorotitanium
  作者：Scot Barry、Andreas Kucht、Homa Kucht、Marvin D. Rausch

  DOI：10.1016/0022-328x(94)05160-d

  日期：1995.3

  (η5-pentaphenylcyclopentadienyl)titanium trichloride (6) in quantitative yield. (η5-N,N-Dimethylaminocyclopentadienyl)titanium trichloride is produced in 54% yield from a reaction between equimolar amounts of (C5H4NMe2)Li and titanium tetrachloride in pentane solution. A reaction between titanium tetrachloride and carbomethoxytrimethylsilycyclopentadiene, formed from (C5H4CO2Me)Na and C1SiMe3, products

  一系列新的官能取代的（η 5 -环戊二烯基）合钛三氯化物和triisopropoxides中描述。（η 5 -Pentaphenylcyclopentadienyl） - （1） -和（η 5 -diphenylphosphinylcyclopentadienyl）三异丙醇钛（2）具有从（C的反应以良好的收率获得5博士5）Na和（C 5 H ^ 4 PPH 2）栗，分别与三异丙氧基氯钛。的治疗1用氯化氢在回流甲苯的形式（η 5 -pentaphenylcyclopentadienyl）三氯化钛（6）定量收率。（η 5 -N，N-二Dimethylaminocyclopentadienyl）三氯化钛在54％产率从等摩尔量的（C之间的反应产生的5 ħ 4 NME 2锂和四氯化钛）的戊烷溶液。四氯化钛和carbomethoxytrimethylsilycyclopentadiene之间的反应中，由（C形成5
• Bidentate metalloligands containing the phosphinocyclopentadienyl ligand. New heterobimetallic complexes and crystal structure of (C5Me5)(C5H4PPh2)Ta(CO)(μ-PPh2)Cr(CO)4
  作者：Cyril Poulard、Gilles Boni、Philippe Richard、Claude Moïse

  DOI：10.1039/a903603b

  日期：——

  Cp*(C5H4PPh2)TaLn [Ln = (H)3, (H)(CO), (H)2(PPh2), (CO)(PPh2)] 2, 3, 4b, 5b containing the diphenylphosphinocyclopentadienyl ligand have been prepared and characterized. The trihydride complex 2 was obtained by reduction of the dichloride compound Cp*(C5H4PPh2)TaCl2 1. Treatment of 2 under a CO atmosphere at 140 °C in decane affords the monohydride complex 3. Compounds 2 and 3 easily react with chlorophosphines

  四种新型金属配体Cp *（C 5 H 4 PPh 2）TaL n [L n  =（H）3，（H）（CO），（H）2（PPh 2），（CO）（PPh 2）]已经制备并表征了包含二苯基膦基环戊二烯基配体的2、3、4b，5b。通过还原二氯化物化合物Cp *（C 5 H 4 PPh 2）TaCl 2获得三氢化物络合物2。1.在140℃的CO气氛中于癸烷中处理2，得到一价氢化物配合物3.化合物2和3容易与氯膦反应，分别产生磷衍生物4b和5b。所有这些金属配体起单齿和/或螯合双齿配体的作用。研究了它们对不饱和有机金属片段[M'（CO）5 ]或[M'（CO）4 ]（M'= Cr，W）的反应性。Cp的X射线晶体结构*（C 5 H ^ 4 PPH 2）的Ta（CO）（μ-PPH 2）C R（CO）4被报告10CR。