Li(1+)*[(η5-C5H4PPh2)W(CO)3](1-) | 165751-18-8

• 英文名称: Li(1+)*[(η5-C5H4PPh2)W(CO)3](1-)
• 英文别名: Li[(η5-C5H4PPh2)W(CO)3]
• CAS: 165751-18-8
• 化学式: C₂₀H₁₄O₃PW*Li
• 分子量: 524.094
• InChiKey: UJWLNVAYMQASCM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Li(1+)*[(η5-C5H4PPh2)W(CO)3](1-) 在 CH₃COOH 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到[(η5-C5H4PPh2)W(CO)3H]
  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
• 作为产物：
  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

• Transition-metal derivatives of the functionalized cyclopentadienyl ligand. XVIII. Syntheses and structures of a series of tetranuclear cyclic complexes [{(CO)3M(μ,η5-C5H4PPh2)}2M′M′′] (M=Cr, Mo or W, M′=M′′=Ag; M=Cr or Mo, M′=M′′=Au; M=Mo, M′=Ag, M′′=Au). Isotopomerism and NMR evidence of a double epimerization process
  作者：Brigitte Brumas-Soula、Françoise Dahan、Rene´ Poilblanc

  DOI：10.1039/a801247d

  日期：——

  Reaction of the lithium salts of the anionic complexes [(η5-C5H4PPh2)M(CO)3]- [M=Cr (1), Mo (2) or W (3)] with AgBF4 or AuClPPh3 easily affords the compounds [(CO)3M(µ,η5-C5H4PPh2)M′]2 [M=Cr, M′=Ag (4); M=Mo, M′=Ag (5); M=W, M′=Ag (6); M=Cr, M′=Au (7); M=Mo, M′=Au (8)], which have been fully characterized by elemental analysis, DCI mass spectrometry, IR, 1H and 31P1H} NMR. X-Ray diffraction studies of the four complexes 4–6 and 8 revealed an eight-membered tetrametallacyclic structure built from two [M′–P–(Cp)–M] sequences [(Cp) being the centroid of the cyclopentadienyl ring] assembled ‘head-to-tail’ by M–M′ metal–metal bonds [dCr–Ag=2.6579(8), dMo–Ag=2.7467(4), dW–Ag=2.7593(5), dMo–Au=2.7146(5) Å], while the observed MπM distances (around 6 Å) exclude any metal–metal interaction. Interestingly, the AgπAg distances in 4 [3.0884(8) Å] and in 5 [3.1780(8) Å], and the AuπAu distance in 8 [3.3755(3) Å], are approximately in the range of metallophilic attractions. These centro-symmetrical molecules 4–8, being composed of two enantiomeric [(CO)3M(µ,η5-C5H4PPh2)M′] fragments, can be considered as meso diastereoisomers. Moreover, the complexes 4, 5 and 6, which include two silver atoms, are formed of the three isotopomers 107Ag–107Ag, 107Ag–109Ag and 109Ag–109Ag, and the variation with temperature of the 31P resonance of 5 suggests that a double epimerization process is operating in these compounds.Formation of 7 and 8 from the reaction of 1 and 2 with AuClPPh3 was also briefly studied. Finally, synthesis of the mixed silver–gold metal complex [(CO)3Mo(µ,η5-C5H4PPh2)}2AgAu] (9) can be achieved in two ways, either by mixing solutions of 5 and 8 or by adding one equivalent of AuClPPh3 to a solution of 5. Synthèses et structures d'une se′rie de compose′s te′trame′talliques [(CO)3M(µ,η5-C5H4PPh2)}2M′M″] (M=Cr, Mo ou W, M′=M″=Ag; M=Cr ou Mo, M′=M″=Au; M=Mo, M′=Ag, M″=Au). Isotopome′rie et mise en e′vidence par RMN d'un processus de double e′pime′risation.La re′action des anions [(CO)3M(η5-C5H4PPh2)]- [M=Cr (1), Mo (2), ou W (3)] à l'e′tat de sels de lithium, avec AgBF4 ou avec AuClPPh3 conduit aise′ment aux compose′s [(CO)3M(µ,η5-C5H4PPh2)M′]2 [M=Cr, M′=Ag (4); M=Mo, M′=Ag (5); M=W, M′=Ag (6); M=Cr, M′=Au (7); M=Mo, M′=Au (8)]. Ceux-ci ont e′te′ entièrement caracte′rise′s par analyse e′le′mentaire, spectrome′trie de masse, IR, RMN 1H et 31P1H}. L'analyse par diffraction des rayons X des quatre compose′s 4–6 et 8 met en e′vidence une structure en couronne, re′sultant de l'association ‘tête à queue’ de deux se′quences [M′–P–(Cp)–M] [(Cp) e′tant le centroïde du cycle cyclopentadienyle] grâce à deux liaisons M–M′ [dCr–Ag=2.6579(8); dMo–Ag=2.7467(4); dW–Ag=2.7593(5); dMo–Au=2.7146(5) Å]. Dans ces compose′s, les distances MπM de l'ordre de 6 Å ne permettent aucune interaction metal–metal, tandis que les distances AgπAg observe′es dans 4 [3.0884(8) Å] et dans 5 [3.1780(8) Å], ainsi que la distance AuπAu dans 8 [3.3755(3) Å], font penser à de possibles interactions ‘metallophiles’. Etant forme′s de deux fragments e′nantiomères [(CO)3M(µ,η5-C5H4PPh2)M′], les complexes te′trame′tallacyclo-octaniques 4 à 8 peuvent être conside′re′s comme des diaste′re′oisomères meso. Les de′rive′s de l'argent 4, 5 et 6 sont par ailleurs constitue′s de trois isotopomères, respectivement 107Ag–107Ag, 107Ag–109Ag et 109Ag–109Ag, et l'e′volution des figures de re′sonance du phosphore 31P de 5 en fonction de la tempe′rature peut être interpre′te′e dans l'hypothèse d'un processus de double e′pime′risation.La formation de 7 et 8 par re′action de 1 et 2 avec AuClPPh3 a e′te′ brièvement e′tudie′e ainsi que celle du complexe mixte argent–or [(CO)3Mo(µ,η5-C5H4PPh2)}2AgAu] (9). Le complexe 9 s'obtient soit en me′langeant des solutions de 5 et de 8, soit en ajoutant un e′quivalent de AuClPPh3 à une solution de 5.

  阴离子配合物[(δ-5-C5H4PPh2)M(CO)3]-[M=Cr (1)、Mo (2)或 W (3)]的锂盐与 AgBF4 或 AuClPPh3 反应，很容易得到化合物 [(CO)3M(µ,δ-5-C5H4PPh2)Mâ²]2[M=Cr, Mâ²=Ag (4)；M=Mo，Mâ²=Ag (5)；M=W，Mâ²=Ag (6)；M=Cr，Mâ²=Au (7)；M=Mo，Mâ²=Au (8)]，这些化合物已通过元素分析、DCI 质谱、红外光谱、1H 和 31P1H} NMR 等方法进行了全面表征。核磁共振。对 4â6 和 8 这四种复合物进行的 X 射线衍射研究表明，它们具有由两个[Mâ²âPâ(Cp)âM]序列（(Cp) 是环戊二烯环的中心点）构成的八元四金属环结构，这两个序列通过 MâMâ² 金属-金属键 "头对尾 "地组装在一起 [dCrâAg=2.6579(8)，dMoâAg=2.7467(4)，dWâAg=2.7593(5)，dMoâAu=2.7146(5) à ]，而观察到的 MÏM 距离（约 6 à ）排除了任何金属与金属之间的相互作用。有趣的是，4[3.0884(8) à ] 和 5 [3.1780(8) à ] 中的 AgÏAg 距离以及 8 [3.3755(3) à ] 中的 AuÏAu 距离近似于亲金属吸引力的范围。这些中心对称分子 4â8 由两个对映体 [(CO)3M(µ,δ-5-C5H4PPh2)Mâ²] 片段组成，可视为中对映异构体。此外，包含两个银原子的配合物 4、5 和 6 是由 107Agâ107Ag、107Agâ109Ag 和 109Agâ109Ag 三种同素异形体形成的，而 5 的 31P 共振随温度的变化表明，这些化合物中存在双重外延化过程。最后，银金混合金属复合物[(CO)3Mo(µ,δ-5-C5H4PPh2)}2AgAu] (9)的合成有两种方法，一种是将 5 和 8 的溶液混合，另一种是在 5 的溶液中加入一个等量的 AuClPPh3。合成[(CO)3M(µ,δ-5-C5H4PPh2)}2M²M²³] (M=Cr, Mo ou W, M²=Mâ³=Ag; M=Cr ou Mo, M²=Mâ³=Au; M=Mo, M²=Ag, Mâ³=Au)化合物及其结构。通过 RMN 测定双重脆化过程的同位素组和证据。阴离子 [(CO)3M(δ-5-C5H4PPh2)]-[M=Cr (1)、Mo (2) 或 W (3)] 在锂溶液中的再反应、avec ou avec AuClPPh3 conduit aiseâ²ment aux composeâ²s [(CO)3M(µ,Î-5-C5H4PPh2)Mâ²]2 [M=Cr, Mâ²=Ag (4)；M=Mo, Mâ²=Ag (5); M=W, Mâ²=Ag (6); M=Cr, Mâ²=Au (7); M=Mo, Mâ²=Au (8)].这些物质通过电子分析、质谱分析、红外光谱、RMN 1H 和 31P1H} 分析获得了不同的特征。L'analyse par diffraction des rayons X des quatre composeâ²s 4â6 et 8 met en eâ²vidence une structure en couronne, reâ²sultant de l'association âtªte à queueâ deux seâ²quences [Mâ²âPâ(Cp)âM] [(Cp) eâ²tant le centro¯de du cycle cyclopentadienyle] gré¢ce à deux liaisons MâMâ² [dCrâAg=2.6579(8); dMoâAg=2.7467(4); dWâAg=2.7593(5); dMoâAu=2.7146(5) à ].在这些成分中，顺序为 6 的 MÏM 距离不允许任何金属与金属之间的相互作用，而在 4 [3.0884(8) ］和 5 [3.1780(8) ］中观察到的 AgÏAg 距离，以及在 8 [3.3755(3) ］中观察到的 AuÏAu 距离，都表明存在可能的 "亲金属 "相互作用。Etant formeâ²s deux fragments eâ²nantiomÃres [(CO)3M(µ,Î-5-C5H4PPh2)Mâ²], les complexes teâ²trameâ²tallacyclo-octaniques 4 à 8 peuvent être considideâ²reâ²s comme des diasteâ²reâ²oisomÃres meso.Les deâriveâ²s de l'argent 4, 5 et 6 sont par ailleurs constitueâ²s de trois isotopomères, respectivement 107Agâ107Ag, 107Agâ109Ag et 109Agâ109Ag、而5号磷31P随温度的变化而发生的共振频率的变化可被解释为一种双重共振过程的假设。通过 1 和 2 与 AuClPPh3 的再反应生成 7 和 8 的过程，以及与之相关的银汞混合物 [(CO)3Mo(µ,Î-5-C5H4PPh2)}2AgAu] (9) 的过程也得到了深入研究。9 号复合物是在 5 号和 8 号溶液的混合溶液中产生的，也可以在 5 号溶液中加入等量的 AuClPPh3。
• Formation of Mo-Pd and W-Pd Complexes. Insight into the Mechanism of Palladium-Catalyzed Metal-Carbon Bond Formation
  作者：Luca Spadoni、Claudio Lo Sterzo、Raffaella Crescenzi、Giuseppe Frachey

  DOI：10.1021/om00007a011

  日期：1995.7

  The oxidative addition of M-I moieties M-I moieties (M = Mo, W) at Pd-O was investigated in order to elucidate the mechanism of palladium-catalyzed metal-carbon bond formation. By the use of metal phosphine-substituted cyclopentadienyl iodo complexes of formula [eta(5)-(Ph(2)P)C5H4](CO)(3)MI (M = Mo, W) it was possible to isolate and characterize a product of oxidative addition to zerovalent palladium, [eta(5)-(Ph(2)P)C5H4](CO)(3)MPd-(PPh(3))I (M = Mo, W).
• Comparison of a range of rhodium-based catalysts for the hydroformylation of selected alkenes
  作者：Ron S. Dickson、Jenna Bowen、Eva M. Campi、W.Roy Jackson、Catrin A.M. Jonasson、Felicity J. McGrath、Daniel J. Paslow、Anastasios Polas、Paul Renton、Serafino Gladiali

  DOI：10.1016/s1381-1169(99)00228-9

  日期：1999.12

  Four rhodium-based catalyst systems (OC)(4)W(mu-PPh2)(2)RhH(CO)(PPh3) 1, (OC)(2)RhMo(CO)(3)(C5H4PPh2) 2, (OC)(2)RhW(CO)(3)(C5H4PPh2) 3. and [Rh(OAc)(2)](2)/PPh3 have been used in the hydroformylation of 1-hexene, styrene and some phosphino-, amino- and amido-alkenes. In general the catalysts showed very similar reactivity and selectivity. (C) 1999 Elsevier Science B.V. All rights reserved.