3,4-Bis-(diphenylphosphino)-5-methoxy-2(5H)-furanon | 56641-92-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: 3,4-Bis-(diphenylphosphino)-5-methoxy-2(5H)-furanon
• 英文别名: 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone；3,4-bis(diphosphenylphosphino)-5-methoxy-2(5H)-furanone；bmf；3,4-bis(diphenylphosphanyl)-2-methoxy-2H-furan-5-one
• CAS: 56641-92-0
• 化学式: C₂₉H₂₄O₃P₂
• 分子量: 482.455
• InChiKey: NUCXHVOYOWQXQP-UHFFFAOYSA-N

物化性质

• 沸点：
  656.6±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(acetonitrile)decacarbonyltriosmium 、 3,4-Bis-(diphenylphosphino)-5-methoxy-2(5H)-furanon 以 二氯甲烷 为溶剂， 以60%的产率得到1,2-Os3(CO)10(3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone)
  参考文献：
  名称：

  Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P–C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO)10(bmf) clusters and HOs3(CO)8(μ-C6H4)[μ-PhPCC(Ph2P)CH(OMe)OC(O)]

  摘要：

  The labile cluster 1,2-Os-3(CO)(10)(MeCN)(2) (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os-3(CO)(10)(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os-3(CO)(10)(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os-3(CO)(10)(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs3(CO)(9)(C29H23O3P2) (3a-c). Thermolysis of HOs3 (CO)(9)(C29H23O3P2) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)(8)(mu-C6H4)(mu-C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated a to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os-3(CO)(10)(diphosphine) derivatives prepared by our groups. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2010.07.003

文献信息

• Ligand substitution behavior of Ru6(μ6-C)(CO)17 with unsaturated diphosphines: facile capping of a polyhedral face and photochemically promoted P–C bond cleavage in the clusterRu6(μ6-C)(CO)14(μ3-bpcd)
  作者：Srikanth Kandala、Casey Hammons、William H. Watson、Xiaoping Wang、Michael G. Richmond

  DOI：10.1039/b915337c

  日期：——

  presence of 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields Ru6(μ6-C)(CO)14(μ3-bpcd) (4) as the sole observable product. Near-UV irradiation of 4 leads to P–C bond cleavage and the formation of phosphido-bridged cluster Ru6(μ6-C)(CO)13[μ3-CC(PPh2)C(O)CH2C(O)](μ-PPh2) (6) in essentially quantitative yield. The reaction between 1 and the ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone

  六钌簇的配体取代化学 茹6（μ 6 -C）（CO）17（1）具有几种不饱和二膦已经研究了配体。热分解1与（Z）-Ph 2 PCH CHPPh 2（dppen）提供新的簇状化合物 茹5（μ 5 -C）（CO）12（μ 3 -dppen）（2），茹6（μ 6 -C）（CO）14（μ 3 -dppen）（3），和茹6（μ 6 -C）（CO）12（μ 3 -dppen）（μ-dppen）（4）。当1和3的混合物时，也可以获得聚类2和3。dppen 用氧化脱羰试剂处理 我3否。热解或我3否在存在1的情况下激活14,5-双（二苯基膦基）-4-环戊烯-1,3-二酮 （光盘）收益 茹6（μ 6 -C）（CO）14（μ 3 -bpcd）（4）作为唯一的可观察产品。的近紫外线照射4根引线至P-C键断裂，并形成磷基-bridged簇的Ru 6（μ 6 -C）（CO）13 [μ 3 -C C（PPH 2）C（O）CH
• Synthesis of the chiral tetrahedral clusters RCCo2NiCp(CO)4(bmf) (R=H, Ph) and thermally promoted diphosphine ligand activation: Regiospecific P–C bond scission and X-ray diffraction structure of Co2NiCp(CO)4[μ2,η2,η1-C(H)CC(PPh2)C(O)OCH(OMe)](μ-PPh2)
  作者：Simon G. Bott、Kaiyuan Yang、Michael G. Richmond

  DOI：10.1016/j.jorganchem.2005.08.040

  日期：2006.1

  η1-C(H)CC(PPh2)C(O)OCH(OMe)](μ-PPh2) include the regioselective cleavage of the P–C(furanone ring) bond, coupled with polyhedral opening of the Co2Ni core and attack on the CpNi center by the other phosphine moiety of the bmf ligand. The diastereoselectivity accompanying the formation of cluster Co2NiCp(CO)4[μ2,η2,η1-C(H)CC(PPh2)C(O)OCH(OMe)](μ-PPh2) is discussed relative to steric effects within the cluster polyhedron

  手性二膦配体3,4-双（二苯基膦基）-5-甲氧基-2（5 H）-呋喃酮（bmf）对混合金属团簇RCCo 2 NiCp（CO）6（R = H，Ph）的控制热解导致CO取代并形成相应的bmf桥簇RCCo 2 NiCp（CO）4（bmf）（R = H，Ph）。这些簇以非对映异构体的非互变混合物形式存在于溶液中，这是通过NMR光谱法确定的。苄二炔封端的簇PhCCo 2 NiCp（CO）4（bmf）在83°C的长时间加热过程中会在1,2-二氯乙烷（DCE）中分解，而HCCo 2 NiCp（CO）4会热分解（BMF），得到新的膦桥接簇钴2 NICP（CO）4 [μ 2，η 2，η 1 -C（H）CC（PPH 2）C（O）OCH（OME）]（μ-PPH 2）在相同条件下。后者的团簇已通过IR和NMR光谱法在溶液中分离和表征，并通过X射线衍射分析确定了固态结构。对于钴结构亮点2 NICP（CO）4 [μ 2，η
• Phosphine Ligand Attack at Both the Methylidyne Cap and the CpNi Center in HCCo₂NiCp(CO)₆ by 2,3-Bis(diphenylphosphino)maleic Anhydride (bma):  P−C Bond Cleavage Reactivity, Kinetics, and X-ray Structures of the Zwitterionic Clusters Co₂NiCp(CO)₄(μ-CO)[μ₂,η²,η¹-C(H)PPh₂CC(PPh₂)C(O)OC(O)] and Co₂NiCp(CO)₄[μ₂,η²,σ-C(H)PPh₂CCC(O)OC(O)](μ₂-PPh₂)
  作者：Simon G. Bott、Kaiyuan Yang、Kathleen A. Talafuse、Michael G. Richmond

  DOI：10.1021/om0209273

  日期：2003.3.1

  Co2Ni core of cluster 3 is structurally similar to 2 and consists of a μ2-PPh2 ligand that spans the Co−Co bond and a Ni−C σ bond resulting from the formal coupling of the maleic anhydride residue with the CpNi moiety. The reaction involving the conversion of 2 to 3 was examined by UV−vis spectroscopy and found to obey first-order kinetics. A rate-limiting step involving dissociative CO loss is supported

  在DCE中，用氧化还原活性的二膦2,3-双（二苯基膦基）马来酸酐（bma）对氢封端的簇HCCo 2 NiCp（CO）6（1）进行热解。80℃提供两性离子簇（2）作为第一个可观察到的产物。团簇2是不稳定的，并且转变成经磷酰基桥连的团簇（3）。团簇2和3均已通过IR和31 P NMR光谱分离并在溶液中表征，而2和3的固态结构均已通过X射线晶体学测定。簇图2显示具有一个Co-Co和Co-Ni键的开放的Co 2 Ni核。bma配体通过PPh 2基团连接到烃基和CpNi部分，Co中心之一拴在bma配体的π键上。打开的钴2簇的镍芯3在结构上类似于2和由μ的2 -PPh 2配体跨越Co的Co键和镍-Cσ键从马来酸酐残基的与正式耦合所得CpNi部分。反应涉及2到3的转化通过紫外可见光谱检查，发现服从一级动力学。甲限速步骤涉及游离CO损失是通过在加入CO的存在下的速率和延迟的激活参数的支持（Δ ħ ⧧ = 31
• Regiospecific and sequential P–C bond activation/cluster transformations in the reaction of PhCCo2MoCp(CO)8 with the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf)
  作者：Simon G. Bott、Kaiyuan Yang、Michael G. Richmond

  DOI：10.1016/j.jorganchem.2006.05.027

  日期：2006.9

  phosphido moiety that bridges the Co–Co vector and a six-electron μ2,η2,η1-C(Ph)CC(PPh2)C(O)OC(O) ligand that caps one of the Co2Mo faces. The X-ray structure of 4 confirms that the five-electron η3,η1,η1- C(Ph)CCC(O)OC(O) ligand is σ-bound to the two cobalt centers in an η1 fashion and π-coordinated to the molybdenum center through a traditional η3-allylic interaction. The reaction between PhCCo2MoCp(CO)8

  混合金属簇PhCCo 2 MoCp（CO）8（1）与二膦配体2,3-双（二苯基膦基）马来酸酐（bma）在CH 2 Cl 2中的热解导致磷桥连簇的顺序形成CO 2 MOCP（CO）5 [μ 2，η 2，η 1 -C（PH）CC（PPH 2）C（O）OC（O）]（μ-PPH 2）（3）和双（膦） -bridged簇共2 MOCP（CO）4 [η 3，η 1，η 1 -C（PH）CCC（O）OC（O）]（μ-PPH 2）2（4）。通过IR和NMR（1 H，13 C和31 P）光谱学分离并表征了图3和图4中的溶液，并通过X射线衍射分析建立了固态结构。两个簇都包含48e-并表现出三角形的Co 2 Mo核。的结构3揭示了膦部分的存在桥接所述Co的Co矢量和六电子μ 2，η 2，η 1 -C（PH）CC（PPH 2）C（O）OC（O）配体覆盖了其中一张Co 2 Mo面。X射线结构图4确认五电子η 3，η
• Yang, Kaiyuan; Bott, Simon G.; Richmond, Michael G., Organometallics, 1995, vol. 14, # 11, p. 4977 - 4979
  作者：Yang, Kaiyuan、Bott, Simon G.、Richmond, Michael G.

  DOI：——

  日期：——