(η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PMe3)2 | 158850-93-2

• 英文名称: (η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PMe3)2
• 英文别名: (η5:η5-C10H8)Mo2(CO)4(PMe3)2H2
• CAS: 158850-93-2
• 化学式: C₂₀H₂₈Mo₂O₄P₂
• 分子量: 586.267
• InChiKey: AETFMZORTPWQHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PMe3)2 以 四氢呋喃 为溶剂， 以80%的产率得到μ-(η5:η5-fulvalene)-bis{dicarbonyl(trimethylphosphine)molybdenum}(Mo-Mo)
  参考文献：
  名称：

  Chemistry of Dinuclear Fulvalene Complexes: Dihydrides, Zwitterions, and Ring-Slippage Complexes Derived from FvM2(CO)6 (M = Mo, W)

  摘要：

  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.

  DOI：

  10.1021/om00020a032
• 作为产物：
  描述：

  (η(5):η(5)-fulvalene)Mo2(CO)6(H)2 、 三甲基膦 以 正己烷 为溶剂， 生成 (η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PMe3)2
  参考文献：
  名称：

  新型膦取代的（富勒烯）二钼羰基氢化物和卤化物的合成与表征

  摘要：

  A number of (fulvalene)dimolybdenum carbonyl dihydrides and dihalides of the general formula FvMo(2)(CO)(4)L(2)X(2) (X = H, L = CO (1a), PPh(3) (1b), PMe(3) (1c); X = Cl, L = CO (2a), PPh(3) (2b), PCy(3) (Cy = cyclohexyl; 2c), PXy(3) (Xy = 3,5-dimethylphenyl; 2d); X = Br, L = CO (3a), PPh(3) (3b), PCy(3) (3c), PXy(3) (3d), PMe(3) (3e); X = I, L = CO (4a), PPh(3) (4b)) have been synthesized and characterized by IR and H-1, C-13{H-1}, and P-31{H-1} NMR spectroscopy and, where possible, by elemental analyses, Spectroscopic data suggest that 2b-d and 3b-e exist solely as cis,cis isomers in solution. cis,cis-4b was also identified but was found to easily transform into a mixture of cis,cis, cis,trans, and trans,trans isomers. Such an interconversion of Ib is fast on the NMR time scale at room temperature. The radical chain halogenation of la,b by activated alkyl halides was found to take place in two distinct steps, involving the intermediate formation of FvMo(2)(CO)(4)L(2)HX (L = CO, X = Cl (5a), Br (6a), I (7a); L = PPh(3), X = Cl (5b), Br (6b), I (7b)). By stepwise addition of different alkyl halides, the hydride-halo complexes 5a, 6a, and 7a were transformed into the mixed dihalides FVMo2(CO)(6)XY (X, Y = Cl, Br (8), Cl, I (9), and Br, I (10)). Mixed dihalides were formed alternatively in halide redistribution reactions between pairs of 2a, 3a, and 4a.

  DOI：

  10.1021/om00009a010

文献信息

• 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.