(η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PPh3)2 | 168841-33-6

• 英文名称: (η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PPh3)2
• CAS: 168841-33-6；169103-27-9；169103-26-8
• 化学式: C₅₀H₄₀Mo₂O₄P₂
• 分子量: 958.693
• InChiKey: PSQSZJWECZGHFH-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：
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反应信息

• 作为反应物：
  描述：

  (η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PPh3)2 在 trityl radical 作用下， 以 苯 为溶剂， 以45%的产率得到trans-(η(5):η(5)-fulvalene)Mo2(CO)4(PPh3)2
  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
• 作为产物：
  描述：

  (η(5):η(5)-fulvalene)Mo2(CO)6(H)2 、 三苯基膦 以 正己烷 为溶剂， 生成 (η(5):η(5)-fulvalene)Mo2(CO)4(H)2(PPh3)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