trans-{molybdenum(0)(carbonyl)4(P(cyclohexyl)3)2} | 54873-46-0

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: trans-{molybdenum(0)(carbonyl)4(P(cyclohexyl)3)2}
• 英文别名: trans-tetracarbonylbis(tricyclohexylphosphine)molybdenum(0)；trans-Mo(CO)4(tricyclohexylphosphine)2；carbon monoxide;molybdenum;tricyclohexylphosphane
• CAS: 54873-46-0
• 化学式: C₄₀H₆₆MoO₄P₂
• 分子量: 768.849
• InChiKey: KNEJKPOWBXXZEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.78
• 重原子数：
  47
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-{molybdenum(0)(carbonyl)4(P(cyclohexyl)3)2} 在 H₂O 、 air 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 以0-30的产率得到
  参考文献：
  名称：

  Bromination of molybdenum carbonyls revisited: oxo complexes and routes to new materials chemistry

  摘要：

  The use of in situ [{MoBr(mu-Br)(CO)(4)}(2)] led to considerably improved preparations of [MoBr2(CO)(3)(PPh(3))(2)] for which the rate of decarbonylation to [MoBr2(CO)(2)(PPh(3))(2)] is greatly increased by refluxing under reduced pressure (15-20 mmHg). Attempts to prepare [MoBr2- (CO)(2){P(C6H11)(3)}(2)] by Br-2 addition to cis- or trans-[Mo(CO)(4){P(C6H11)(3)}(2)] led to [HP(C6H11)(3)][Mo-(=0)Br(4)L] [L = OP(C6H11)(3) or H2O]. The OP(C6H11)(3) complex maybe used as a catalyst for the epoxidation of cyclohexene or for the addition of singlet oxygen to alpha-terpinene (1-isopropyl-4-methylcyclohexa-1, 3-diene). The species [HP(C6H11)(3)] [Mo(=0)Br-4{OP(C6H11)(3)}] was adsorbed onto sodium montmorillonite in a new type of reaction for sodium montmorillonite involving multiple abstractions of NaBr from the complex anion. In solution [HP(C6H11)(3)][Mo(=0)Br-4{OP(C6H11)(3)}] also decomposes to crystalline [Mo(=0)(2)Br-2{OP(C6H11)(3)}(2)] which is monoclinic, space group C2/c [a = 27.15(5), b = 8.486(8), c = 18.49(2) Angstrom, beta = 110.94(7)degrees].

  DOI：

  10.1039/dt9950001489
• 作为产物：
  描述：

  molybdenum hexacarbonyl 、 三环己基膦 以 异辛烷 为溶剂， 生成 trans-{molybdenum(0)(carbonyl)4(P(cyclohexyl)3)2}
  参考文献：
  名称：

  Mo 催化末端烯烃 Z-2 选择性异构化的氢化物迁移机制

  摘要：

  由于E烯烃的热力学偏好，末端烯烃选择性异构化为 Z - 2 -烯烃具有挑战性。这项工作研究了 Mo 催化剂对一系列脂肪族烯烃实现高Z选择性的机制。DFT 分析指出氢化物迁移是异构化过程的关键。

  DOI：

  10.1002/cctc.202301052

文献信息

• Reversible hydrogen adsorption at room temperature using a molybdenum–dihydrogen complex in the solid state
  作者：Kaiji Uchida、Naoki Kishimoto、Shin-ichiro Noro、Hiroaki Iguchi、Shinya Takaishi

  DOI：10.1039/d1dt01404h

  日期：——

  present H2 adsorption properties of the 16-electron precursor complex ([Mo(PCy3)2(CO)3]) in the solid state synthesized by two procedures. One is the direct synthesis under an Ar atmosphere (1), and the other is removal of the N2-adduct under vacuum (2). 2 showed ideal Langmuir type reversible ad/desorption of H2 above room temperature, whereas 1 showed irreversible adsorption. The adsorption enthalpy

  温和条件下的可逆 H 2储存是材料化学领域最重要的目标之一。二氢配合物是该目标的有吸引力的材料，因为它们具有适中的吸附焓以及不裂解 H-H 键的吸附。尽管有这些优点，但固态二氢配合物的H 2吸附研究很少。我们在此展示了通过两种方法合成的固态16 电子前体复合物（[Mo(PCy 3 ) 2 (CO) 3 ]）的H 2吸附特性。一种是在 Ar 气氛下直接合成 ( 1 )，另一种是去除 N 2-真空加合物（2）。2在室温以上显示出理想的朗缪尔型 H 2可逆吸附/解吸，而1显示出不可逆吸附。的吸附焓2比在THF溶液大。使用 DFT 计算，这种差异可以通过固态中不存在激动相互作用来解释。
• Pentabenzylcyclopentadienyl molybdenum and tungsten hydrides: Syntheses, structures and electrochemistry of [MHCpBz(CO)2(L)] (L=CO, PMe3, PPh3)
  作者：M. Augusta Antunes、Sónia Namorado、Cristina G. de Azevedo、M. Amélia Lemos、M. Teresa Duarte、José R. Ascenso、Ana M. Martins

  DOI：10.1016/j.jorganchem.2010.02.012

  日期：2010.5

  Complexes [MHCpBz(CO)2(PR3)] (R = CH3, M = Mo (1); M = W (2); R = Ph, M = Mo (3); CpBz = C5(CH2Ph)5) were prepared by thermal decarbonylation of the corresponding [MHCpBz(CO)3] in the presence of trimethyl- or triphenyl-phosphine. In solution the NMR spectra of all compounds show the presence of cis and trans isomers that interconvert at room temperature. In the solid state the molecular structures

  配合物[MHCP Bz（CO）2（PR 3）]（R = CH 3，M = Mo（1）; M = W（2）; R = Ph，M = Mo（3） ; CP Bz  = C 5（通过在三甲基或三苯基膦的存在下将相应的[MHCP Bz（CO）3 ]进行热脱羰制备CH 2 Ph）5）。在溶液中，所有化合物的NMR光谱均显示在室温下相互转化的顺式和反式异构体的存在。在固态下，化合物1和2的分子结构对应于反式异构体，而对于3则存在顺式异构体。 的[MoHCP电化学的Bz（CO）2（PME 3）]（1），[MoHCP的Bz（CO）3 ]（5），[WHCP的Bz（CO）3 ]（6），[WCP的Bz（CO）3描述了] 2（7）和[MCa href=https://www.molaid.com/MS_6449 target="_blank">CP Bz（CO）3（CH 3 CN）] BF 4（8）。M-H键的裂解在氧化或还原时发生。阳离子[MCa href=https://www.molaid.com/MS_6449 target="_blank">CP Bz（CO）2 L（CH 3 CN）] +[MHCP Bz（CO）2 L]（L
• Five-co-ordinate molybdenum and tungsten complexes, [M(CO)3(PCy3)2], which reversibly add dinitrogen, dihydrogen, and other small molecules
  作者：Gregory J. Kubas

  DOI：10.1039/c39800000061

  日期：——

  New complexes of molybdenum and tungsten with dinitrogen and other small molecules, trans-[M(CO)3(PCy3)2L](L = N2, H2, C2H4, or SO2), have been synthesized by the reaction of [M(CO)3(cycloheptatriene)] with 2PCy3 in the presence of L; removal of L yields the formally five-co-ordinate species [M(CO)3(PCy3)2].

  合成了钼和钨与二氮和其他小分子的新配合物，反式-[M（CO）3（PCy 3）2 L]（L = N 2，H 2，C 2 H 4或SO 2）在L存在下通过[M（CO）3（环庚三烯）]与2PCy 3的反应；去除L会产生形式上为五坐标的物质[M（CO）3（PCy 3）2 ]。
• <i>cis</i>-Tetracarbonylbis(tricyclohexylphosphine)molybdenum(0) and pentacarbonyl(tricyclohexylphosphine)molybdenum(0)
  作者：Jose E. Cortes-Figueroa、Madeline S. Leon-Velazquez、Johanna Ramos、Jerry P. Jasinski、David A. Keene、Jeffrey D. Zubkowski、Edward J. Valente

  DOI：10.1107/s0108270100013111

  日期：2000.12.15

  In the present redetermination of the complex cis-tetra-carbonylbis(tricyclohexylphosphine)molybdenum(0), (I), [Mo(C18H33P)(2)(CO)(4)] or cis-eta (1)-[P(C6H11)(3)](2)}Mo(CO)(4), the Mo atom has a distorted octahedral geometry with a large PD Mo-P angle of 104.8 (1)degrees. A strong trans influence on the carbonyls in (I) is seen in a shortening of the Mo-C and a lengthening of the C-O distances opposite the phosphines compared with those that are cis. This influence is greatly diminished in the complex pentacarbonyl(tricyclohexylphosphine)molybdenum(0), (II), [Mo(C18H33P)(CO)(5)] or eta (1)-[P(C6H11)(3)]}Mo(CO)(5), the core of which has a slightly distorted C-4 nu geometry.
• A case of severe steric aggravation: X-ray structural analysis of cis-Mo(CO)4(PCy3)2 (CY = cyclo-C6H11)
  作者：Marcus Watson、Simon Woodward、Gráinne Conole、Margalith Kessler、Georgia Sykara

  DOI：10.1016/s0277-5387(00)88162-0

  日期：1994.8

  Despite being extremely sterically congested the molecule cis-Mo(CO)(4)(PCy(3))(2) is readily synthesized and characterized by X-ray crystallography which reveals that the primary method of relieving the steric strain is by substantial increase of the molybdenum-phosphorus bond distances [Mo-P-av = 2.654(4) Angstrom].