(η5:η5-C10H8)W2(CO)6H2 | 105160-08-5

• 英文名称: (η5:η5-C10H8)W2(CO)6H2
• 英文别名: (fulvalene)W2(H)2(CO)6
• CAS: 105160-08-5
• 化学式: C₁₆H₁₀O₆W₂
• 分子量: 665.952
• InChiKey: NEEOXZVZKCLWDI-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：

  (η5:η5-C10H8)W2(CO)6H2 在 I₂ 作用下， 以 乙醚 为溶剂， 以>99的产率得到(η(5):η(5)-fulvalene)W2(CO)6I2
  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：

  (η5:η5-C10H8)W2(CO)6D2 在 SiO₂/H₂O 作用下， 以 水 为溶剂， 生成 (η5:η5-C10H8)W2(CO)6H2
  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

文献信息

• Synthesis and characterization of FvW2(CO)4L2(SR)2 (L=CO, PPh2Me; R=H, i-Pr, CH2Ph, Ph) type (fulvalene)tungsten dihydrosulfides and dithiolates
  作者：István Kovács、Alan Shaver

  DOI：10.1016/s0022-328x(99)00158-8

  日期：1999.7

  FvW2(CO)4(PPh2Me)2(SR)2 (R=i-Pr, CH2Ph, Ph), upon treatment with RSphthalimide. FvW2(CO)4(PPh2Me)2(SPh)2 was converted into FvW2(CO)4(PPh2Me)2(SH)2 under an atmosphere of H2S. All PPh2Me-substituted dithiolato complexes as well as the bishydrosulfide derivative exist in solution as an equilibrium mixture of d,l- and meso-cis,cis, cis,trans and trans,trans isomers. However, only the cis,cis isomer of the

  的（等人直接，高产率合成4 N）2 [FVW 2（CO）6 ]，其中的Fv =η 5：η 5 -C 10 ħ 8（富瓦烯），从W（CO）3（EtCN）3报道了Li 2 [C 10 H 8 ]和Et 4 NBr。它与硫转移试剂RSphthalimide（R = i -Pr ，CH 2 Ph，Ph）反应，得到相应的二硫代lato配合物FvW 2（CO）6（SR）2。处理硫代巯基配合物，其中R = i-Pr，CH 2 Ph与CS 2经由混合的RSW（CO）3（μ-Fv）（CO）2 WS 2 CSR中间体得到噻吨酸酯衍生物FvW 2（CO）4（S 2 CSR）2。不稳定的双氢硫化氢络合物FvW 2（CO）6（SH）2是通过混合的氢-氢硫化氢中间体FvW 2（CO）6（SH）H从FvW 2（CO）6 H 2和S 8获得的。FVW 2（CO）6 ħ 2还与PPh 2 Me反应，得到配体取代的产物FvW
• Synthesis and Crystal Structures of (Fulvalene)W₂(SH)₂(CO)₆, (Fulvalene)W₂(μ-S₂)(CO)₆, and (Fulvalene)W₂(μ-S)(CO)₆:  Low Valent Tungsten Carbonyl Sulfide and Disulfide Complexes Stabilized by the Bridging Fulvalene Ligand
  作者：Kenneth B. Capps、Glenn D. Whitener、Andreas Bauer、Khalil A. Abboud、Ian M. Wasser、K. Peter C. Vollhardt、Carl D. Hoff

  DOI：10.1021/ic025590b

  日期：2002.6.1

  Reaction of FvW(2)(H)(2)(CO)(6) with 2/8S(8) in THF results in rapid and quantitative formation of FvW(2)(SH)(2)(CO)(6). The crystal structure of this complex is reported and shows that the two tungsten-hydrosulfide groups are on opposite faces of the fulvalene ligand in an anti configuration. Nevertheless, treatment of FvW(2)(SH)(2)(CO)(6) (1) with PhN[double bond]NPh produces FvW(2)(mu-S(2))(CO)(6)

  FvW（2）（H）（2）（CO）（6）与2 / 8S（8）在THF中的反应导致FvW（2）（SH）（2）（CO）（6）的快速定量形成。据报道该络合物的晶体结构，表明两个钨-氢硫化物基团以反构型位于富瓦烯配体的相对面上。不过，用PhN [双键] NPh处理FvW（2）（SH）（2）（CO）（6）（1）会产生FvW（2）（mu-S（2））（CO）（6）（ 2）和Ph（H）NN（H）Ph。还描述了桥接二硫化物的晶体结构，该结晶与1以2：1的比例共结晶。将2当量的* CrCp *（CO）（3）暴露于1会产生类似的H原子转移，从而生成2 HCrCp *（CO）（3）和2。尝试从该反应混合物衍生的溶液中获得后者的晶体，第三产物FvW（2）（mu-S）（CO）（6）（3），通过晶体学分析。