hexacarbonyl-μ-η5:5-fulvalene-ditungsten

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: hexacarbonyl-μ-η5:5-fulvalene-ditungsten
• 化学式: C₁₆H₈O₆W₂
• 分子量: 663.936
• InChiKey: PGZQPQBSFAZUDL-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：

  hexacarbonyl-μ-η5:5-fulvalene-ditungsten 在 H₂ 作用下， 以 not given 为溶剂， 以0%的产率得到(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
• 作为产物：
  描述：

  (η5:η5-C10H8)W2(CO)6H2 以 二氧六环-d8 为溶剂， 以>95的产率得到hexacarbonyl-μ-η5:5-fulvalene-ditungsten
  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

• Use of the Electron-Reservoir [Fe^ICp(arene)] Sandwiches as Efficient and Selective Electrocatalysts:  Syntheses of Homo- and Heterodinuclear Zwitterionic Transition-Metal Fulvalene Complexes
  作者：David S. Brown、Marie-Hélène Delville、K. Peter C. Vollhardt、Didier Astruc

  DOI：10.1021/om960003d

  日期：1996.4.30

  in THF for the electron-transfer-chain-catalyzed (electrocatalyzed) synthesis of the homobimetallic zwitterions [(CO)3M-FvM+(CO)2(PR3)2] (M = Mo, W; Fv = μ2-η10-fulvalene; R = Me, OMe) from [M2Fv(CO)6] and PR3 and of the heterobimetallic zwitterions [(CO)3MIFvM2(CO)(PR3)2] (M1 = Mo, W; M2 = Fe, Ru) from [M1M2Fv(CO)5] and PR3. Cyclic voltammetry (CV) experiments (DMF, 0.1 M n-Bu4NBF4, Pt, 0.400 V s-1)

  电子贮存器配合物的[Fe我的Cp（C 6 H ^ 6）]，[铁我的Cp（C 6我6）]和[铁我的Cp *（C 6我6）]（CP =η 5 -C 5 ħ 5 ;的Cp * =η 5 -C 5我5）已被用来作为引发剂，在THF为homobimetallic两性离子的电子转移链催化（电催化）合成[（CO）3中号-有限体积法+（CO）2（PR 3）2 ]（M = Mo，W; Fv =μ2 -η 10 -fulvalene; [M 2 Fv（CO）6 ]和PR 3以及异双金属两性离子[（CO）3 M I FvM 2（CO）（PR 3）2 ]中的R = Me，OMe）（M 1 = Mo，W; [M 1 M 2 Fv（CO）5 ]和PR 3中的M 2 = Fe，Ru）。循环伏安法（CV）实验（DMF，0.1 M n -Bu 4 NBF 4，Pt，0.400 V s -1）表明在PR 3（R = Me，O
• 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
• Brown, David S.; Delville-Desbois, Marie-Helene; Boese, Roland, Angewandte Chemie, 1994, vol. 106, p. 715 - 717
  作者：Brown, David S.、Delville-Desbois, Marie-Helene、Boese, Roland、Vollhardt, K. Peter C.、Astruc, Didier

  DOI：——

  日期：——
• First photosubstitution chemistry of fulvalene-bridged metal-metal bonded carbonyls. Synthesis and structural determination of novel homo- and heterobimetallic alkyne complexes
  作者：James S. Drage、Mats Tilset、K. Peter C. Vollhardt、Timothy W. Weidman

  DOI：10.1021/om00083a032

  日期：1984.5
• Abrahamson, Harmon B.; Heeg, Mary Jane, Inorganic Chemistry, 1984, vol. 23, # 15, p. 2281 - 2286
  作者：Abrahamson, Harmon B.、Heeg, Mary Jane

  DOI：——

  日期：——