(η(5):η(5)-fulvalene)Mo2(CO)5(PMe3) | 99267-62-6

• 英文名称: (η(5):η(5)-fulvalene)Mo2(CO)5(PMe3)
• CAS: 99267-62-6
• 化学式: C₁₈H₁₇Mo₂O₅P
• 分子量: 536.184
• InChiKey: LVCVJSFFUYCPOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：

  (η(5):η(5)-fulvalene)Mo2(CO)5(PMe3) 、 三甲基膦 以 四氢呋喃 为溶剂， 以0%的产率得到
  参考文献：
  名称：

  （富勒烯）五羰基二钼二膦：双核有机金属两性离子

  摘要：

  DOI：

  10.1021/om00131a033
• 作为产物：
  描述：

  在 CF₃COOH 作用下， 以 四氢呋喃 为溶剂， 生成 (η(5):η(5)-fulvalene)Mo2(CO)5(PMe3)
  参考文献：
  名称：

  （富勒烯）五羰基二钼二膦：双核有机金属两性离子

  摘要：

  DOI：

  10.1021/om00131a033

文献信息

• Chemistry of Dinuclear Fulvalene Complexes: Dihydrides, Zwitterions, and Ring-Slippage Complexes Derived from FvM2(CO)6 (M = Mo, W)
  作者：Mats Tilset、K. Peter C. Vollhardt、Roland Boese

  DOI：10.1021/om00020a032

  日期：1994.8

  Reduction of the metal-metal-bonded complex FvW2(CO)6 generated the dianion FvW2(CO)62-. An X-ray crystallographic analysis of [Et4N+]2[FvW2(CO)6]2- (monoclinic space group P2(1)/c, a = 7.687(2) angstrom, b = 13.752(4) angstrom, c = 16.297(5) angstrom, beta = 94.80(2)-degrees, V = 1716.8(8) angstrom3, Z = 4) showed the dianion to contain a planar Fv ring system bonded to the two metal centers in an anti fashion. The dianion reacted with a number of electrophiles to yield the neutral species FVW2(CO)6E2 (E = H, Me, Et, sigma-C3H5, CH2Ph). The pK(a) values for the two consecutive deproteinations of FvW2(CO)rH2 were determined as 14.0 and 16.6 by equilibrium measurements in acetonitrile. Thermolysis and photolysis of FvW2(CO)6H2 yielded FvW2(CO)6 and H-2. Unlike Cp2W2(CO)6, FvW2(CO)6 underwent protonation at the W-W bond by HBF4-Et2O in acetonitrile. Reactions of FvW2(CO)6 and FvMo2(CO)6 with PMe3 and Me2PCH2PMe2 (dmpm) resulted in generation of the dinuclear zwitterions FvM2(CO)5(PMe3)2 and FvM2(CO)5)(dmpm), respectively. An X-ray crystallographic analysis of FvMo2(CO)5 (orthorhombic space group P2(1)2(1)2(1), a = 9.1049(8) angstrom, b = 12.2598(14) angstrom, c = 20.1606(18) angstrom, V = 2250.4(7) angstrom3, Z = 4) showed an anti coordination of the MO(CO)3- and Mo(CO)2(dmpm)+ moieties at a planar Fv ligand. Electrophiles added at the anionic part of the zwitterions, whereas LiAlH4 effected reduction of coordinated CO to CH3 at the cationic center of FvMo2(CO)5(PMe3)2. Excess PMe3 caused the conversion of FvMo2(CO)5(PMe3)2 and FvMo2(CO)5)(dmpm) to Mo(CO)3(PMe3)3 along with FvMo(CO)2(PMe3)2 and FvMo(CO)2(dmpm), respectively. These reactions constitute the first ring-slippage reactions that have been observed in fulvalene metal complexes. When treated with Mo(CO)3(NCMe)3, FvMo(CO)2(PMe3)2 cleanly regenerated FvMo2(CO)5(PMe3)2.
• Designed syntheses of heterobimetallic fulvalene complexes
  作者：Mark A. Huffman、David A. Newman、Mats Tilset、William B. Tolman、K. Peter C. Vollhardt

  DOI：10.1021/om00140a038

  日期：1986.9
• Synthesis and Characterization of Mo-Mo-Bonded (Fulvalene)dimolybdenum Carbonyl Complexes Containing Sterically Demanding Phosphines
  作者：Istvan Kovacs、Michael C. Baird

  DOI：10.1021/om00009a011

  日期：1995.9

  The new metal-metal-bonded (fulvalene)dimolybdenum carbonyl complexes FVMo2(CO)(4)L(2) (L = PPh(3), PCy(3), PXy(3); Xy = 3,5-dimethylphenyl) were synthesized via (af hydride hydrogen atom abstraction from FVMo2(CO)(4)L(2)H(2) (L = PPh(3), PXy(3)) by trityl radicals, (b) sodium reduction of FVMo2(CO)(4)L(2)Cl(2) (L = PPh(3), PCy(3), PXy(3)), and (c) oxidation of the dianions [FVMo2(CO)(4)L(2)](2-) (L = PPh(3), PCy(3)). The compounds were characterized by IR, UV-vis, and H-1, C-13H-1} and P-31H-1} NMR spectroscopy, and the spectroscopic data are in all cases consistent with structures containing the phosphines in positions trans to the Mo-Mo bond. The UV-vis spectra of trans-FvMo(2)(CO)(4)L(2) (L = PPh(3), PCy(3), PXy(3)) all exhibit a sigma --> sigma* transition at 374 nm, suggesting that the phosphines influence neither sterically nor electronically the Mo-Mo bond strength. Evidence for radical intermediates was found when FvMo(2)(CO)(4)(PPh(3))(2) was prepared from FvMo(2)(CO)(4)(PPh(3))(2)H-2.