(η(5):η(5)-fulvalene)Mo2(CO)6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (η(5):η(5)-fulvalene)Mo2(CO)6
• 英文别名: (CpMo(CO)3)2
• 化学式: C₁₆H₈Mo₂O₆
• 分子量: 488.116
• InChiKey: PMXNHSCUDGZFIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (η(5):η(5)-fulvalene)Mo2(CO)6 以 further solvent(s) 为溶剂， 以0%的产率得到(η5:η5-fulvalene)dimolybdenum tetracarbonyl
  参考文献：
  名称：

  （富瓦烯）六羰基二钼的化学性质：刚性固定的双核过渡金属配合物

  摘要：

  DOI：

  10.1021/om00133a019
• 作为产物：
  描述：

  (η(5):η(5)-fulvalene)Mo2(CO)6(H)2 在 trityl radical 作用下， 以 正己烷 、 苯 为溶剂， 生成 (η(5):η(5)-fulvalene)Mo2(CO)6
  参考文献：
  名称：

  含立体键位的膦的钼钼钼键合（富勒烯）二钼羰基配合物的合成与表征

  摘要：

  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-13{H-1} and P-31{H-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.

  DOI：

  10.1021/om00009a011

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.
• Efficient syntheses of new fulvalene-bridged carbonyl complexes of cobalt, ruthenium, chromium, molybdenum, and tungsten
  作者：K. Peter C. Vollhardt、Timothy W. Weidman

  DOI：10.1021/om00079a016

  日期：1984.1
• (Fulvalene)dimolybdenum pentacarbonyl diphosphine: a dinuclear organometallic zwitterion
  作者：Mats Tilset、K. Peter C. Vollhardt

  DOI：10.1021/om00131a033

  日期：1985.12
• Boese, Roland; Tolman, William B.; Vollhardt, K. Peter C., Organometallics, 1986, vol. 5, # 3, p. 582 - 584
  作者：Boese, Roland、Tolman, William B.、Vollhardt, K. Peter C.

  DOI：——

  日期：——
• New General Synthetic Strategy of Fulvalene Homodinuclear Zwitterions. Electrochemical Behavior of (η:⁵η⁵-(C₅H₃CO₂Me)₂)Mo₂(CO)₆R₂ (R = I, Me)
  作者：Consuelo Moreno、M. Luisa Marcos、M. José Macazaga、Rosa M. Medina、David H. Farrar、Jaime González-Velasco、Salomé Delgado

  DOI：10.1021/om980269f

  日期：1998.10.1

  The reaction of Li-2[eta(5):eta(5);(C5H3CO2Me)(2))Mo-2(CO)(6)] (from trans-(eta(5):eta(5)-(C5H3CO2Me)(2))Mo-2-(CO)(6)) (1) with MeI yields (eta(5):eta(5)-(C5H3CO2Me)(2))Mo-2(CO)(6)Me-2 (3). The reaction of cis-(eta(5):eta(5)-(C5H3CO2Me)(2))Mo-2(CO)(6) (2) with I-2 leads to the formation of (eta(5):eta(5)-(C5H3CO2Me)(2))Mo-2(CO)(6)I-2 (4). The X-ray structure of 4 has been determined; The reactions of 1 with P-donor nucleophiles (PPhMe2, PPh2Me, P(n-Bu)(3), and PMe3) and (eta(5):eta(5)-(C10H8)M-2(CO)(6) (M = Mo and W) with PMe3, in the presence of 1 equiv of Me3NO, produce CO labilization and formation of the dinuclear zwitterions (eta(5):eta(5)-(C5H3CO2Me)(2))Mo-2(CO)(5)L-2 and (eta(5):eta(5)-(C10H8)M-2(CO)(5)(PMe3)(2) (M = Mo and W) 5, 6, 7, 8, 9, and 10, respectively). The dimer [(eta(5)-C5H4CO2Me)Mo(CO)(3)](2) (11) was obtained by reaction of Mo(CO)(6) with sodium carbomethoxy cyclopentadienide in THF followed by oxidation with ferric sulfate. The reaction of 11 with PPh2Me in the presence of 1 equiv of Me3NO gives the disproportionation species [(eta(5)-C5H4CO2Me)Mo(CO)(2)(PPh2Me)(2)(+)][eta(5)-C5H4CO2Me)Mo(CO)(3)(-)] (12). The electrochemical study of 3 and 4 is reported. Two distinct cathodic waves are observed in the voltammetric reduction of 4, the less negative one with a coupled anodic peak at high sweep rate in PC.