phenylphosphine pentacarbonylmolybdenum(0) | 72868-86-1

• 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: phenylphosphine pentacarbonylmolybdenum(0)
• 英文别名: Carbon monoxide;molybdenum;phenylphosphane
• CAS: 72868-86-1
• 化学式: C₁₁H₇MoO₅P
• 分子量: 346.087
• InChiKey: FSIBZJMVQYSVBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.0
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phenylphosphine pentacarbonylmolybdenum(0) 在 potassium hydroxide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  3H-Benzophosphepine Complexes:  Versatile Phosphinidene Precursors

  摘要：

  The synthesis of a variety of benzophosphepine complexes [R = Ph, t-Bu, Me; MLn = W(CO)(5), Mo(CO)(5), Cr(CO)(5), Mn(CO)(2)Cp] by two successive hydrophosphinations of 1,2-diethynylbenzene is discussed in detail. The first hydrophosphination step proceeds at ambient temperature without additional promoters, and subsequent addition of base allows full conversion to benzophosphepines. Novel benzeno-1,4-diphosphinanes were isolated as side products. The benzophosphepine complexes themselves serve as convenient phosphinidene precursors at elevated, substituent-dependent temperatures (> 55 degrees C). Kinetic and computational analyses support the proposal that the phosphepine-phosphanorcaradiene isomerization is the rate-determining step. In the absence of substrate, addition of the transient phosphinidene to another benzophosphepine molecule is observed, and addition to 1,2-diethynylbenzene furnishes a delicate bidentate diphosphirene complex.

  DOI：

  10.1021/ja054885w
• 作为产物：
  描述：

  molybdenum hexacarbonyl 以 四氢呋喃 、 乙醚 、 乙腈 为溶剂， 生成 phenylphosphine pentacarbonylmolybdenum(0)
  参考文献：
  名称：

  Marinetti, Angela; Bauer, Siegfried; Ricard, Louis, Organometallics, 1990, vol. 9, # 3, p. 793 - 798

  摘要：

  DOI：

文献信息

• Phosphepines:  Convenient Access to Phosphinidene Complexes
  作者：Mark L. G. Borst、Rosa E. Bulo、Christiaan W. Winkel、Danièle J. Gibney、Andreas W. Ehlers、Marius Schakel、Martin Lutz、Anthony L. Spek、Koop Lammertsma

  DOI：10.1021/ja050817y

  日期：2005.4.1

  o-diethynylbenzene with transition metal-complexed primary phosphines gives in a single base-induced step stable phosphepine complexes as confirmed by X-ray data. At 75-80 degrees C these phosphepines undergo clean cheletropic elimination of naphthalene to give transient carbene-like phosphinidene complexes that can be trapped in high yield by alkenes, alkynes, and alcohols.

  X 射线数据证实，邻二乙炔苯与过渡金属络合的伯膦反应在单一的碱诱导步骤中得到稳定的膦配合物。在 75-80 摄氏度时，这些磷化氢会经历萘的清洁螯合消除，以产生瞬态的卡宾状磷化烯配合物，这些配合物可以被烯烃、炔烃和醇以高产率捕获。
• Substitution of chloride in [PtCl2(dppe)] by the chiral anionic ligand [Mo(CO)5(PPhH)]− : Synthesis and X-ray structure of [Pt(μ-PPhH)2{Mo(CO)5}2(dppe)] and a 31P{1H} NMR analysis of its isomeric products and fluxionality
  作者：Antony J. Deeming、Simon Doherty

  DOI：10.1016/0277-5387(95)00321-5

  日期：1996.4

  Abstract Reaction of the chiral anionic ligand [Mo(CO)5(PPhH)]− with [PtCl2(L-L)] affords the neutral trimetallic monophosphido bridged complexes [Pt(μ-PPhH)2Mo-(CO)5}2(L-L)] (L-L = dppe, Ph2PCH2CH2PPh2, 2; dpae, Ph2AsCH2CH2AsPh2, 3; dppe′, cis-Ph2PCH=CHPPh2, 4). Compounds 2–4 are the first examples of heterometallic complexes that contain two chiral primary phosphido bridges existing as pairs of

  摘要手性阴离子配体[Mo（CO）5（PPhH）]-与[PtCl2（LL）]反应，得到中性三金属单磷酸桥连络合物[Pt（μ-PPhH）2 Mo-（CO）5} 2（ LL）]（LL = dppe，Ph2PCH2CH2PPh2，2; dpae，Ph2AsCH2CH2AsPh2，3; dppe'，顺式-Ph2PCH = CHPPh2，4）。化合物2-4是杂金属配合物的第一个实例，该配合物包含两个作为非对映异构体对存在的手性初级磷酸桥。[Pt（μ-PPhH）2 Mo（CO）5} 2（dppe）]（2）已通过光谱法和单晶X射线分析进行了表征。2的分子结构可以视为与一个螯合dppe和两个阴离子膦配体键合的Mo2Pt磷酸桥联三聚体或方形PtII络合物。后面的PtP4描述成功解释了在2–4的31P 1H} NMR光谱中观察到的谱线加宽，从围绕Pt-磷酸键的受限旋转产生的几种相互转换的旋转异构体形式可以理解这一点。PtPMo角为122
• Baacke, Michael; Morton, Stephen; Johannsen, Gerd, Chemische Berichte, 1980, vol. 113, # 4, p. 1328 - 1342
  作者：Baacke, Michael、Morton, Stephen、Johannsen, Gerd、Weferling, Norbert、Stelzer, Othmar

  DOI：——

  日期：——
• An improved and one-step synthesis of phosphido-bridged tetracobalt carbonyl cluster, Co4(CO)8(μ2-CO)2(μ4-PC6H5)2
  作者：Biau-Hung Chang

  DOI：10.1016/s0020-1693(00)93542-4

  日期：1982.1
• Substitution of chloride in [PtCl2(PET3)2] by the chiral anionic ligand [Mo(CO)5(PPhH)]− to give mixed platinum-molybdenum compounds and a 31P∗1H∗ NMR analysis of their fluxionality. X-ray crystal structure of [PtCl(PEt3)2 (μ-PPhH) ∗Mo(CO)5∗] and trans-[Pt(PEt3)2 (μ-PPH)2 ∗Mo(CO)5∗2]
  作者：Antony J. Deeming、Bruce R. Cockerton、Simon Doherty

  DOI：10.1016/s0277-5387(96)00403-2

  日期：1997.3

  Deprotonation of the primary phosphine complex [Mo(CO)(5)(PPhH(2))] generated [Mo(CO)(5)(PPhH)](-), a chiral anionic ligand which reacted readily with cis- or trans-[PtCl2(PEt(3))(2)] via facile nucleophilic substitution of one or both chloride ligands to afford trans-[PtCl(PEt(3))(2)(mu-PPhH)Mo(CO)(5)}] (1) and cis- and trans-[Pt(PEt(3))(2)(mu-PPhH)(2)MO(CO)(5)}(2)] (2), respectively. These are rare examples of heterometallic complexes containing primary phosphido bridges, Compound 1 can be described either as the square-planar Pt-II complex with the anionic ligand PPhHMo(CO)(5)}(-) or as the Pt-Mo phosphido-bridged dimer trans- [PtCl(PEt(3))(2)(mu-PPhH)Mo(CO)(5)}]. As a phosphido-bridged heterobimetallic 1 possesses an exceptionally large Pt-P-Mo angle [120.9(1)degrees] reflecting the long Pt-Mo nonbonding interaction (4.5 Angstrom). Compound 2 can correspondingly be described either as a phosphido-bridged PtMo2 trimer or a square-planar arrangement of two neutral PEt(3) and two anionic PPhH Mo(CO)(5)} ligands at Pt. The low-temperature P-31H-1} NMR spectrum of 1 showed several ABXY spin systems together with their associated ABXYM (M = Pt-195) counterparts and variable-temperature studies revealed the dynamic interconversion of several rotametric isomers arising from restricted relation about the Pt-P mu bond. The P-31H-1} NMR spectrum of trans-2 shows its two possible RR/SS and meso diastereoisomers, the latter existing in clearly identifiable rotameric forms which interconvert slowly at -75 degrees C. We note very different values between (2)J(P-P) and (1)J(Pt-195-P) for th, anionic ligands [PPhHMo(CO)(5)}](-) and PEt(3), unattributable to bond length variation but which must reflect reduced s-orbital contribution to the Pt-P bond of the anionic phosphines PPhH Mo(CO)(5)}. (C) 1997 Elsevier Science Ltd.