Dimethyl-(5-methylfuran-2-yl)-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane | 501651-98-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Dimethyl-(5-methylfuran-2-yl)-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane
• 英文别名: dimethyl-(5-methylfuran-2-yl)-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane
• CAS: 501651-98-5
• 化学式: C₁₆H₂₄OSi
• 分子量: 260.451
• InChiKey: ZBEQRXXGCAGLQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  13.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Lu(trimethylsilylmethyl)3(tetrahydrofuran)2 、 Dimethyl-(5-methylfuran-2-yl)-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane 以 正戊烷 为溶剂， 以24%的产率得到[Lu(η5-C5Me4SiMe2(C4H2MeO-2))((trimethylsilyl)methyl)2(THF)]
  参考文献：
  名称：

  Ring-Opening of a Furyl Group Appended to the Cyclopentadienyl Ligand in Rare-Earth Metal Half-Sandwich Complexes

  摘要：

  A series of scandium, lutetium, and yttrium complexes containing a tetramethylcyclopentadienyl ligand with a pendant furyl group, [Ln{eta(5)-C5Me4SiMe2(C4H2RO-2)}(CH2SiMe3)(2)(THF)] (Ln = Sc, Lu, Y; R = H, Me), have been synthesized and structurally characterized. Single-crystal X-ray diffraction studies of the scandium complexes [Sc{eta(5)-C5Me4SiMe2(C4H2RO-2)}(CH2SiMe3)(2)(THF)] (R = H, Me) revealed a pseudo-four-coordinate metal center without additional coordination of the furyl group. The previously elusive lutetium complex [Lu{eta(5)-C5Me4SiMe2(C4H2MeO-2)}(CH2SiMe3)(2)(THF)] could be isolated and exhibited structural features analogous to those of the scandium compound. Variable-temperature H-1 NMR spectroscopic studies of the entire series confirmed the labile nature of both the THF ligands and furyl donor in solution. Rates for the ring-opening reaction, triggered by intramolecular C-H bond activation, were shown to depend primarily on the metal size. The ring-opening reaction resulted in the formation of the corresponding dinuclear yne-enolate complexes [Ln{eta(5):eta(1)-C5Me4SiMe2(CCCHCRO)}(CH2SiMe3)](2) (Ln = Sc, Lu, Y; R = H, Me). Substitution at the 5-furyl position did not markedly influence the rate of the ring-opening reaction but shifted the position of the monomer-dimer equilibrium toward the monomer. Only a large excess of THF allowed the observation of monomeric yne-enolate complexes such as [Y{eta(5):eta(1)-C5Me4SiMe2(CCCHCHO)}(CH2SiMe3)(THF)(2)], which was characterized by X-ray crystallography. Addition of THF increased the stability of the lutetium bis(alkyl) complexes and allowed the formation of the corresponding cationic compounds by treatment with [NEt3H][BPh4] to yield [Lu{eta(5):eta(1)-C5Me4SiMe2(C4H2RO-2)}(CH2SiMe3)(THF)(n)][BPh4] (Ln = Lu; R = H, Me), which resisted ring- opening of the furyl group.

  DOI：

  10.1021/om0701726

文献信息

• Alkyl Complexes of Rare-Earth Metals That Contain a Furyl-Functionalized Cyclopentadienyl Ligand:  Alkyl Cation Formation and Unexpected Ring-Opening Reaction of the Furyl Group
  作者：Stefan Arndt、Thomas P. Spaniol、Jun Okuda

  DOI：10.1021/om0207010

  日期：2003.2.1

  Rare-earth metal complexes of the type [Lnη5:η1-C5Me4SiMe2(C4H3O-2)}(CH2SiMe3)2(THF)] (Ln = Y, Lu) were prepared by σ-bond metathesis of [Ln(CH2SiMe3)3(THF)2] with the 2-furyl-functionalized tetramethylcyclopentadiene (C5Me4H)SiMe2(C4H3O-2) and isolated as colorless crystals. Single-crystal X-ray structure analysis of the lutetium complex confirmed the coordination of the furyl group and THF to give

  的类型的稀土类金属配合物[LN η 5：η 1 -C 5我4森达2（C 4 H ^ 3 O-2）}（CH 2森达3）2（THF）]（Ln为Y，路）是通过[Ln（CH 2 SiMe 3）3（THF）2 ]与2-呋喃基官能化的四甲基环戊二烯（C 5 Me 4 H）SiMe 2（C 4 H 3O-2）并分离为无色晶体。complex配合物的单晶X射线结构分析证实了呋喃基和THF的配位产生了一个三角形的双锥体几何分子，其供氧原子位于顶端。氧供体原子的不稳定性导致通量行为。与THF中的三苯基硼烷的反应，得到热鲁棒单（烷基）阳离子[LN η 5：η 1 -C 5我4森达2（C 4 H ^ 3 O-2）}（CH 2森达3）（THF）Ñ ] +。出乎意料的是，[Ln（CH 2 SiMe 3）的反应3（THF）2 ]与5甲基呋喃基官能化的四甲基环戊二烯（C 5我4 1H）森达2 （C 4 H ^ 2的