[(η5-C5H3)2(SiMe2)2]Fe2(CO)2(μ-CO)2 | 138784-76-6

• 英文名称: [(η5-C5H3)2(SiMe2)2]Fe2(CO)2(μ-CO)2
• 英文别名: bis(μ-carbonyl)dicarbonyl{cis-μ-((1)9-12-η:3-7-η)-2,2,8,8-tetramethyl-2,8-disilatricyclo{7.3.0.0(3,7)}dodeca-3,5,9,11-tetraene-1,7-diyl}diiron(I)；[(η⁵-C₅H₃)₂(SiMe₂)₂]Fe₂(CO)₂(μ-CO)₂；(SiMe2)(SiMe2)[(η(5)-C5H3)Fe(CO)]2(μ-CO)2
• CAS: 138784-76-6
• 化学式: C₁₈H₁₈Fe₂O₄Si₂
• 分子量: 466.204
• InChiKey: IHYPCLAGMBGIMP-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-C5H3)2(SiMe2)2]Fe2(CO)2(μ-CO)2 、 三乙基硼氢化锂 以 甲苯 为溶剂， 反应 1.0h， 以26%的产率得到
  参考文献：
  名称：

  Structures and reactivity of doubly-bridged dicyclopentadienyl dinuclear iron complexes

  摘要：

  The molecular structure of the doubly-bridged bis(cyclopentadienyl) diiron complex [(eta(5)-C5H3)(2) (SiMe2)(2)]Fe-2(CO)(2)(mu-CO)(2) (1b) was determined, and compared with that of the other analogue [(eta(5)-C5H3)(2)(CMe2)(SiMe2)]Fe-2(CO)(4) (1a). The former involves two bridging and two terminal carbonyls, and a normal Fe-Fe bond distance, while the latter contains all-terminal carbonyls and a longer than normal Fe-Fe bond distance. The possible reason for different coordination modes is discussed. Complexes (1a-b) react with I-2 to give the corresponding diiodo products [(eta(5)-C5H3)(2)(EMe2)(SiMe2)]Fe-2(CO)(4)I-2 (E = C, 2a; E = Si, 2b) and with phenylacetylene to give the bridging mu-C=CHPh products [(eta(5)-C5H3)(2) (EMe2)(SiMe2)]Fe-2(CO)(2)(mu-CO)(mu-C=CHPh) (3a-b). Reaction of 1a with Na/Hg, then with MeI yields the unexpected desilylated product [(eta(5)-C5H4)(2)(CMe2)][Fe(CO)(2)Me](2) (5a). Reaction of 1b with LiBHEt3 affords the bridging methylene product [(eta(5)-C5H3)(2)(SiMe2)(2)]Fe-2(CO)(2)(mu-CO)(mu-CH2) (6b). The molecular structures of 2a and 3b were also determined by X-ray diffraction. (C) 2014 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.01.027
• 作为产物：
  描述：

  五羰基铁 在 (Si(CH₃)2C₅H₄)2 作用下， 以 甲基环己烷 为溶剂， 以2.2%的产率得到[(η5-C5H3)2(SiMe2)2]Fe2(CO)2(μ-CO)2
  参考文献：
  名称：

  双桥环戊二烯基配体的双核金属配合物

  摘要：

  Binuclear metal complexes derived from the doubly bridged cyclopentadiene system 2,2,8,8-tetramethyl-2,8-disilatricyclo[7.3.0.0(3,7)]dodeca-3,5,9,11-tetraene (LH2) are examined. This compound is deprotonated with 2 equiv of 1-butyllithium to form the dilithio salt LLi2 (2). Reaction of 2 with trimethyltin chloride yields (Me3Sn)2L (3). The analogous reaction with Cp*RuCl (Cp* = C5Me5) gives the binuclear ruthenocene (Cp*Ru)2L (4). By cocomplexation of 2 and Cp*Li with iron(II) chloride, the binuclear ferrocene (Cp*Fe)2L (5) is obtained. Reaction of LH2 with octacarbonyldicobalt leads to the formation of [(CO)2Co]2L (6). The analogous reaction with pentacarbonyliron yields a mixture of products, from which [(CO)2Fe]2L (Fe-Fe) (7) is isolated. The stereochemistry of complexes 3-7 is investigated by IR and NMR spectroscopy. Single-crystal X-ray structure determinations are performed for 5 and 6. The structure investigations on 5 show a trans arrangement of the two Cp*Fe units. The ligand L is not planar. The unit cell contains two independent molecules, whose bonding parameters are essentially identical (crystal system triclinic; space group P1BAR; a = 8.7443 (13), angstrom, b = 18.561 (3) angstrom, c = 20.576 (4) angstrom; alpha = 89.340 (13)-degrees, beta = 89.160 (13)-degrees, gamma = 78.300 (12)-degrees; Z = 4). The structure investigations on the cis isomer of 6 also show a nonplanar ligand L (crystal system monoclinic; space group P2(1)/n; a = 10.496 (2) angstrom, b = 13.380 (2) angstrom, c = 14.537 (6) angstrom; beta = 92.96 (3)-degrees; Z = 4). The flexibility of L is estimated, and the potential of its binuclear complexes for catalytic processes is discussed.

  DOI：

  10.1021/om00039a043

文献信息

• Synthesis and structures of doubly bridged bis(cyclopentadienyl) tetracarbonyl diiron complexes
  作者：Shansheng Xu、Jianyong Zhang、Bolin Zhu、Baiquan Wang、Xiuzhong Zhou、Linhong Weng

  DOI：10.1016/s0022-328x(01)00697-0

  日期：2001.4

  A series of doubly bridged bis(cyclopentadienyl) tetracarbonyl diiron complexes (7–13) have been synthesized by the reaction of the corresponding ligand (1–6) with Fe(CO)5 in refluxing xylene. It is unusual that the reaction of ligand (GeMe2)(GeMe2)(C5H4)2 (3) with Fe(CO)5 gave the complex (GeMe2)[(η5-C5H4)Fe(CO)]2(μ-CO)2 (10) as the main product which lost the GeMe2, only a small amount of the expected

  一系列双桥联双（环戊二烯基）四羰二铁配合物（的7 - 13）已经由相应的配体（反应合成1 - 6以Fe（CO）2）5在回流的二甲苯。这是不寻常的是配位体的反应（GEME 2）（GEME 2）（C 5 H ^ 4）2（3）为Fe（CO）5，得到复合体（GEME 2）[（η 5 -C 5 H ^ 4）的Fe （CO）] 2（μ-CO）2（10），其失去了GEME主要产物2，仅预期产物少量（GEME 2）2 [（η 5 -C 5 H ^ 3）的Fe（CO）] 2（μ-CO）2（9）中的溶液获得。的分子结构9和（森达2森达2）2 [（η 5 -C 5 H ^ 3）的Fe（CO）] 2（μ-CO）2（13）已被X-射线衍射来确定。
• Reactions of Doubly SiMe₂-Bridged Bis(cyclopentadienyl) Complexes of Molybdenum and Iron Carbonyls: Competitive Ring-to-Metal Migrations of Hydrogen and SiMe₂
  作者：Bolin Zhu、Yunfei Chen、Wei Shi、Yuan Li、Xiaoting Hao

  DOI：10.1021/om300305g

  日期：2012.5.28

  Reaction of the doubly bridged bis(cyclopentadiene) (C5H4(SiMe2))2 (1) with Mo(CO)6 in refluxing xylene gave the corresponding dinuclear molybdenum carbonyl complex [(η5-C5H3)2(SiMe2)2]Mo2(CO)6 (3) and the desilylated product [(η5-C5H4)2(SiMe2)]Mo2(CO)6 (6), together with the singly SiMe2SiMe2-bridged dinuclear molybdenum product [(η5-C5H4)2(SiMe2SiMe2)]Mo2(CO)6 (5) and the novel complex [(SiMe2)(η5-C5H4)Mo(CO)3]2

  所述双桥联双反应（环戊二烯）（C 5 H ^ 4（森达2））2（1）用的Mo（CO）6在回流的二甲苯，得到相应的双核钼羰基络合物[（η 5 -C 5 H ^ 3）2（森达2）2 ]的Mo 2（CO）6（3）和脱甲硅基化产物[（η 5 -C 5 H ^ 4）2（森达2）]的Mo 2（CO）6（6），与单独使用森达一起2森达2 -bridged双核钼产物[（η 5 -C 5 H ^ 4）2（森达2森达2）]的Mo 2（CO）6（5）和新的配合物[（森2）（η 5 -C 5 H ^ 4）的Mo（CO）3 ] 2（4）含有两个沫-Si键。产物的这种多样性是由氢和SiMe 2的类似的环到金属迁移能力引起的群体及其在反应过程中的竞争性迁移。的二氢化物反应的顺式- [（η 5 -C 5 H ^ 3）2（森达2）2 ]的Mo 2（CO）6（H）2（图7C）在回流的二甲苯也得到上述产品，除了4，这表明图7c