(η(5)-Cp)Mo(CO)2(PPh3)(H) | 33519-69-6

• 英文名称: (η(5)-Cp)Mo(CO)2(PPh3)(H)
• 英文别名: CpMo(CO)2(PPh3)H；η5-C5H5Mo(CO)2PPh3H；CpMo(CO)2(H)(PPh3)；HMo(CO)2(PPh3)(Cp)；(dicarbonyl)(cyclopentadienyl)(triphenylphosphine)molybdenum hydride；trans-HMo(CO)2(PPh3)(Cp)
• CAS: 33519-69-6；31884-23-8；32011-66-8
• 化学式: C₂₅H₂₁MoO₂P
• 分子量: 480.354
• InChiKey: LYNPIIJMDRCEFG-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：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (η(5)-Cp)Mo(CO)2(PPh3)(H) 在 四氯化碳 作用下， 生成 (η-C5H5)Mo(CO)2(PPh3)Cl
  参考文献：
  名称：

  Suenkel, Karlheinz; Ernst, Herbert; Beck, Wolfgang, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1981, vol. 36, # 4, p. 474 - 481

  摘要：

  DOI：
• 作为产物：
  描述：

  (η5-C5H5)Mo(CHMe(OMe))(CO)2(PPh3) 以 正己烷 、 二氯甲烷 为溶剂， 以28%的产率得到(η(5)-Cp)Mo(CO)2(PPh3)(H)
  参考文献：
  名称：

  Formation of the alkoxyalkyl complexes [M{CHMe(OMe)}(CO)₂(η-C₅H₄R)](M = Mo, R = H; M = W, R = H or Me) and their transformations by loss of MeOH into η³-propenoyl or vinyl complexes. Crystal structures of [Mo{CHMe(PPh₃)}(CO)₂(PPh₃)(η-C₅H₅)]BF₄, [Mo(η³-CH₂CHCO)(CO)(PPh₃)(η-C₅H₅)] and [W(σ-CHCH₂)(CO)₂(PPh₃)(η-C₅H₄Me)]

  摘要：

  Addition of MeSO3F or [Me3O]BF4 followed by PPh3 to the aldehyde complex [Mo(MeCHO)(CO)2(eta-C5H5)]- results in formation of the methoxyalkyl complex trans-[Mo{CHMe(OMe)}(CO)2(PPh3)(eta-C5H5)] in a reaction that proceeds via the unstable [Mo{eta-2-CHMe(OMe)}(CO)2(eta-C5H5)]. A by-product of this reaction is the ylide trans-[Mo{CHMe(PPh3)}(CO)2(PPh3)(eta-C5H5)]X (X = BF4- or SO3F-), a species (X = BF4) better prepared by treatment of trans-[Mo{CHMe(OMe)}(CO)2(PPh3)(eta-C5H5)] with HBF4 in the presence of PPh3. The crystalline ylide trans-[Mo{CHMe(PPh3)}(CO)2(PPh3)(eta-C5H5)]BF4 is monoclinic, with a = 11.378(34), b = 18.903(35), c = 20.17(8) angstrom, beta = 115.28(31)-degrees and for the 3918 independent reflections with I/sigma(I) > 3.0, R = 0.0510. In solution, trans-[Mo{CHMe(OMe)}(CO)2(PPh3)(eta-C5H5)] either degrades to [MoH(CO)2(PPh3)(eta-C5H5)] or loses MeOH to form the eta-3-propenoyl [Mo(eta-3-CH2CHC = O)(CO)(PPh3)(eta-C5H5)]. This molecule is monoclinic, with a = 17.231(50), b = 8.189(14), c = 16.727(36) angstrom, beta = 106.79(22)-degrees and for the 1654 independent reflections for which \F\/sigma(\F\) > 4.0, R = 0.100. The proposed mechanism for its formation is based on isotopic tracking experiments and includes a vinyl to carbonyl migration. Treatment of [WMe(CO)3(eta-C5H4R)] (R = H or Me) with PPh3 in MeCN gives the acyl [W(sigma-COMe)(CO)2(PPh3)(eta-C5H4R)]. These react with [Me3O][BF4] to form the cationic carbenes [W{ = CMe(OMe)}(CO)2(PPh3)(eta-C5H4R)]BF4, which in turn react with LiBHEt3 to give the alkoxyalkyls trans-[W{CHMe(OMe)}(CO)2(PPh3)(eta-C5H4R)]. The alkoxyalkyls trans-[W{CHMe(OMe)}(CO)2(PPh3)(eta-C5H4R)] react with traces of acid to form the sigma-vinyls trans-[W(sigma-CH = CH2)(CO)2(PPh3)(eta-C5H4R)], the methylcyclopentadienyl species of which is crystalline, monoclinic, with a = 36.952(40), b = 10.971(13), c = 25.148(23) angstrom and beta = 103.60(8)-degrees. For the 2542 independent reflections for which \F\/sigma(\F\) > 5.0, R converged to 0.0750.

  DOI：

  10.1039/dt9910001117

文献信息

• Hydride Transfer Reactions of Transition Metal Hydrides:  Kinetic Hydricity of Metal Carbonyl Hydrides
  作者：Tan-Yun Cheng、Bruce S. Brunschwig、R. Morris Bullock

  DOI：10.1021/ja9820036

  日期：1998.12.1

  Hydride transfer from neutral transition metal hydrides (MH) to Ph3C+BF4- gives M-FBF3 and Ph3CH. The rate law −d[Ph3C+BF4-]/dt = k[Ph3C+BF4-][MH] was established from kinetic measurements using stopped-flow methods. Second-order rate constants determined in CH2Cl2 solution at 25 °C range from kH− = 7.2 × 10-1 M-1 s-1 to kH− = 4.6 × 106 M-1 s-1. The order of increasing kinetic hydricity is (C5H4CO2Me)(CO)3WH

  从中性过渡金属氢化物 (MH) 到 Ph3C+BF4- 的氢化物转移得到 M-FBF3 和 Ph3CH。速率定律 -d[Ph3C+ -]/dt = k[Ph3C+ -][MH] 是根据使用停流方法的动力学测量建立的。在 25 °C 的 CH2Cl2 溶液中测定的二阶速率常数范围从 kH− = 7.2 × 10-1 M-1 s-1 到 kH− = 4.6 × 106 M-1 s-1。增加动力学水合度的顺序是 (C5H4CO2Me)(CO)3WH < (CO)5MnH < Cp*(CO)3CrH < Cp(CO)3WH < HSiEt3 < cis-(CO)4(PCy3)MnH < cis-(CO) )4(PPh3)MnH < (C5H4Me)(CO)3WH < Cp(CO)3MoH < Cp*(CO)3WH < (茚基)(CO)3WH < (CO)5ReH < Cp*(CO)3MoH
• Chemistry of the thermally generated, molybdenum-centered radicals {η5-C5H5Mo(CO)2L} (L = CO, PPh3)
  作者：Philip R. Drake、Michael C. Baird

  DOI：10.1016/0022-328x(89)88046-5

  日期：1989.3

  compounds [η5-C5H5Mo(CO)2L]2 (L = CO, PPh3) exist in solution solely as the metalmetal bonded dimers. no chemical evidence being found for the presence of small equilibrium amounts of the corresponding monomers η5-C5H5Mo(CO)2L}. However, the latter are readily synthesized via hydrogen atom abstraction by the trityl radical from the hydrides η5-C5H5Mo(CO)2LH. The thus-formed radicals are very reactive and

  与此相反，以他们的铬类似物，化合物[η 5 -C 5 H ^ 5的Mo（CO）2 L] 2（L = CO，PPH 3）存在于溶液中单独用作metalmetal连接的二聚体。无化学证据被发现的小型平衡量的相应单体η的存在5 -C 5 H ^ 5的Mo（CO）2 L}。然而，后者可容易地通过氢原子夺取由三苯甲基从氢化物η自由基合成5 -C 5 H ^ 5的Mo（CO）2LH。如此形成的自由基具有很高的反应性，并且除了二聚作用外，它们还参与了各种原子提取和配体取代反应。对这些反应的产物分布的分析为十七电子中间体的中间体提供了明确的证据。
• Synthesis and chemistry of a bridging vinylidenedicobalt complex. Evidence for a nonchain radical mechanism in its reaction with metal hydrides to give heteronuclear clusters
  作者：Eric N. Jacobsen、Robert G. Bergman

  DOI：10.1021/ja00293a037

  日期：1985.4

  La reaction des especes [CpCo(CO)] 2 Na avec le dibromo-1,1 ethylene donne le complexe (μ-CCH 2 )(CpCoCO) 2 (1) dont on etudie la structure. Sa protonation donne [(μ-CCH 3 )(CpCoCO) 2 ] + BF 4 − instable, se decomposant en [(μ 3 -CCH 3 )(Cp 2 Co 3 CO) 2 ] + BF 4 − . Le complexe (1) reagit avec CpMo(CO) 2 (L)H pour donner (μ 3 -CCH 3 )(μ 2 -CO)(CpCo) 2 [CpMo(CO) 2 ]. Structure cristalline

  La 反应特异 [CpCo(CO)] 2 Na avec le dibromo-1,1 ethylene donne le complexe (μ-CCH 2 )(CpCoCO) 2 (1) 不涉及结构。Sa 质子化 [(μ-CCH 3 )(CpCoCO) 2 ] + BF 4 - 不稳定，se 分解剂 en [(μ 3 -CCH 3 )(Cp 2 Co 3 CO) 2 ] + BF 4 - 。Le complexe (1) reagit avec CpMo(CO) 2 (L)H倒入donner (μ 3 -CCH 3 )(μ 2 -CO)(CpCo) 2 [CpMo(CO) 2 ]。结构结晶
• Catalysts for hydrogenation and hydrosilylation, methods of making and using the same
  申请人：Brookhaven Science Associates, LLC

  公开号：US06737531B1

  公开（公告）日：2004-05-18

  A compound is provided including an organometallic complex represented by the formula I: [CpM(CO)2(NHC)Lk]+A−  I wherein M is an atom of molybdenum or tangsten, Cp is substituted or unsubstituted cyclopentadienyl radical represented by the formula [C5Q1Q2Q3Q4Q5], wherein Q1 to Q5 are independently selected from the group consisting of H radical, C1-20 hydrocarbyl radical, substituted hydrocarbyl radical, halogen radical, halogen-substituted hydrocarbyl radical, —OR, —C(O)R′, —CO2R′, —SiR′3 and —NR′R″, wherein R′ and R″ are independently selected from the group consisting of H radical, C1-20 hydrocarbyl radical, halogen radical, and halogen-substituted hydrocarbyl radical, wherein said Q1 to Q5 radicals are optionally linked to each other to form a stable bridging group, NHC is any N-heterocyclic carbene ligand, L is either any neutral electron donor ligand, wherein k is a number from 0 to 1 or L is an anionic ligand wherein k is 2, and A− is an anion. Processes using the organometallic complex as catalyst for hydrogenation of aldehydes and ketones are provided. Processes using the organometallic complex as catalyst for the hydrosilylation of aldehydes, ketones and esters are also provided.

  提供了一种化合物，其中包括由公式I表示的有机金属配合物：[CpM(CO)2(NHC)Lk]+A−  I，其中M是钼或钨原子，Cp是由公式[C5Q1Q2Q3Q4Q5]表示的取代或未取代的环戊二烯基基团，其中Q1至Q5分别独立地选自H基团、C1-20烃基基团、取代烃基基团、卤基基团、卤代烃基基团、—OR、—C(O)R′、—CO2R′、—SiR′3和—NR′R″的基团，其中R′和R″分别独立地选自H基团、C1-20烃基基团、卤基基团和卤代烃基基团，其中所述的Q1至Q5基团可以选择地相互连接以形成稳定的桥接基团，NHC是任何N-杂环卡宾配体，L是任何中性电子给体配体，其中k是从0到1的数字，或L是一个带负电的配体，其中k为2，A−是一个阴离子。提供了使用该有机金属配合物作为醛和酮的加氢催化剂的过程。还提供了使用该有机金属配合物作为醛、酮和酯的加硅烷化催化剂的过程。
• Catalytic ionic hydrogenations of ketones using molybdenum and tungsten complexesBased on the presentation given at Dalton Discussion No. 4, 10–13th January 2002, Kloster Banz, Germany.
  作者：Mark H. Voges、R. Morris Bullock

  DOI：10.1039/b107754f

  日期：2002.2.15

  Cp(CO)2(PR3)MH to Ph3C+BAr′4− [Ar′ = 3,5-bis(trifluoromethyl)phenyl] in the presence of 3-pentanone. These ketone complexes are catalyst precursors for hydrogenation of Et2CO under mild conditions (23 °C, <4 atm H2). Analogous catalytic hydrogenations are obtained from reaction of the PCy3 complexes Cp(CO)2(PCy3)MH with Ph3C+BAr′4−. The proposed mechanism involves displacement of the ketone by H2, producing

  酮络合物[CPM（CO）2（PR 3）（η 1 -Et 2 ç O）] + BAR' 4 -（R =苯基或Me; M = Mo或W）从氢化物转移制备来自CP（CO）2（PR 3）MH至pH 3 ç +巴' 4 - [中，Ar'= 3,5-双（三氟甲基）苯基]在3-戊酮的存在。这些酮络合物是在温和条件下（23°C，<4 atm H 2）加氢Et 2 C O的催化剂前体。从PCy 3配合物CP（CO）的反应获得类似的催化氢化2（PCY 3）MH的Ph 3 Ç +巴' 4 - 。所提出的机理涉及通过H 2置换酮，产生阳离子金属二氢化物[CPM（CO） 2（PR 3）（H） 2 ] +。从二氢转移质子得到质子化的酮，然后从中性金属氢化物CPM（CO） 2（PR 3）H转移氢，生成醇配合物[CPM（CO） 2（PR 3）（Et 2 CHOH）] +。游离醇产物通过H置换而从金属中释放出来2或酮，完成