(η(5):η(5)-fulvalene)W2(CO)6I2 | 65979-88-6

• 英文名称: (η(5):η(5)-fulvalene)W2(CO)6I2
• 英文别名: diiodohexacarbonyl(fulvalene)ditungsten(W-W)
• CAS: 65979-88-6
• 化学式: C₁₆H₈I₂O₆W₂
• 分子量: 917.745
• InChiKey: VSTHKMQXDAJFTM-UHFFFAOYSA-L

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)W2(CO)6I2 、 三环己基膦 在 Me₃NO 作用下， 以 四氢呋喃 为溶剂， 以95%的产率得到cis,cis-(η(5):η(5)-fulvalene)W2(CO)4I2(PCy3)2
  参考文献：
  名称：

  带有（P-供体）亲核试剂的（富瓦烯）二钨羰基卤化物和环戊二烯基钨羰基卤化物配合物的合成新方法

  摘要：

  的（η反应5：η 5 -C 10 ħ 8 W）2（CO）6我2和（η 5 -C 5 H ^ 5）W（CO）3我与P-供体亲核体（L = P（OME ）3，PPhMe 2，P（n- Bu）3，PPh 2 Me，P（p- tol）3，P（m- tol）3和PCy 3）分别存在2和1当量我3 NO产量（η 5：η 5-C 10 ħ 8）w 2（CO）4大号2我2和（η 5 -C 5 H ^ 5）W（CO）2 LI，分别作为一个混合物顺式/反式异构体。这些异构体的相对比例取决于膦配体的立体电子性质。的（η的X射线结构5：η 5 - （C 10 H ^ 8）w 2（CO）6我2已被确定。

  DOI：

  10.1021/om980180+
• 作为产物：
  描述：

  hexacarbonyl-μ-η5:5-fulvalene-ditungsten 在 碘甲烷 作用下， 以 二氯甲烷 为溶剂， 生成 (η(5):η(5)-fulvalene)W2(CO)6I2
  参考文献：
  名称：

  Abrahamson, Harmon B.; Heeg, Mary Jane, Inorganic Chemistry, 1984, vol. 23, # 15, p. 2281 - 2286

  摘要：

  DOI：

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.