1,1-methyl(phenyl)-1-sila-[1]ferrocenophane | 155892-94-7

• 英文名称: 1,1-methyl(phenyl)-1-sila-[1]ferrocenophane
• 英文别名: 1-methyl-1-phenyl-sila-[1]ferrocenophane；(1,1'-ferrocenediyl)methylphenylsilane；[1]silaferrocenophane；(PhMeSi(C5H5)2)Fe
• CAS: 155892-94-7
• 化学式: C₁₇H₁₆FeSi
• 分子量: 304.247
• InChiKey: XHCITHOBBGTRFJ-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：

  1,1-methyl(phenyl)-1-sila-[1]ferrocenophane 以 neat (no solvent, solid phase) 为溶剂， 以46%的产率得到
  参考文献：
  名称：

  Solid state polymerization of the unsymmetrical [1]ferrocenophane Fe(η-C5H4)2SiMePh; synthesis of the first stereoregular organometallic polymer

  摘要：

  [1]二茂铁 Fe(β-C5H4)2SiMePh 的固态聚合产生了立构规整聚(二茂铁基甲基苯基硅烷)，这是立构规整有机金属聚合物的第一个例子。

  DOI：

  10.1039/a801042k

文献信息

• Synthesis, Structure, and Ring-Opening Polymerization (ROP) of a Phosphonium-Bridged [1]Ferrocenophane
  作者：Timothy J. Peckham、Alan J. Lough、Ian Manners

  DOI：10.1021/om980696t

  日期：1999.3.1

  phosphorus-bridged [1]ferrocenophanes, (η-C5H4)2FeP(S)Ph (5a), (η-C5H4)2FeP[Fe(CO)4]Ph (6), and [(η-C5H4)2FePFpPh][PF6] (7) (where Fp = (η-C5H5)Fe(CO)2), were investigated with respect to their ring-opening polymerization (ROP) behavior. Only compound 10b was found to undergo ROP, which occurred both thermally and in the presence of a transition-metal catalyst (PtCl2). The resultant ionomeric polymer [(η-C5H4)2FePPhMe][OTf]}n

  稳定的鏻桥连[1]二茂铁基[（η-C 5 H ^ 4）2 FEPPhMe] [光学传递函数（图10b）通过的反应中合成的磷桥连[1]二茂铁基（η-C 5 H ^ 4）2 FEPPh（3a）与三氟甲磺酸甲酯（MeOTf）。10b的单晶X射线衍射研究显示，环戊二烯基环平面之间的夹角为24.4（5）°，小于3a的相应夹角（26.7°）。化合物10b和许多其他四配位，磷桥联的[1]二茂铁（（-C 5 H 4）2FEP（S）PH（图5a），（η-C 5 H ^ 4）2 FEP的[Fe（CO）4 ] Ph（上6），和[（η-C 5 H ^ 4）2 FEPFpPh] [PF 6 ]（7）（式中：Fp =（η-C 5 H ^ 5）的Fe（CO）2），分别相对于它们的开环聚合（ROP）的行为的影响。发现仅化合物10b经历了ROP，其在热和过渡金属催化剂（PtCl 2）的存在下均发生。将所得的离聚物[（η-C
• Highly Active Cationic Rhodium(I) Precatalysts for the Ambient Temperature Ring-Opening Polymerization of [1]Silaferrocenophanes and Tetramethyldisilacyclobutane
  作者：Karen Temple、Sebastian Dziadek、Ian Manners

  DOI：10.1021/om020492j

  日期：2002.10.1

  with the rhodium complex (9 mol %), which resulted in Cp−Si bond cleavage affording ferrocene as the sole, isolable product. The presence of 1,5-cod inhibited the catalytic activity of both [Rh(1,5-cod)2]OTf and [Rh(1,5-cod)(dmpe)]PF6, suggesting that elimination of a 1,5-cod ligand is necessary to generate the true active catalytic species. The addition of dmpe effectively arrested the catalytic activity

  阳离子铑（I）配合物的[Rh（1,5-COD）2 ] A（A =光学传递函数，PF 6，1,5- COD = 1,5-环辛二烯）已被证明表现出过渡高催化活性金属介导的开环聚合的（ROP）硅桥联[1] ferrocenophanes（例如，fcSiMe 2（1A），FC =铁（η 5 -C 5 H ^ 4）2），以定量得到高分子量（中号n > 10 5）聚二茂铁基硅烷（例如[fcSiMe 2 ] n（2a））。然而，所得的聚二茂铁溶液长时间暴露于催化剂导致分子量显着下降。用[Rh（1,5-cod）2 ] OTf形成高分子量聚碳硅烷均聚物（7）（M n = 4.20×10 ），也证明过渡金属催化的四甲基二硅环环丁烷（6）的ROP以及该物质与1a的共聚是可行的。5到1.08×10 6，PDI = 1.39-2.08）和聚（carbosilane- ř -ferrocenylsilane）（8）共聚物（中号ñ
• 1-Sila-[1]ferrocenophanes, structure and reactivity
  作者：Bernd Wrackmeyer、Anahid Ayazi、Wolfgang Milius、Max Herberhold

  DOI：10.1016/s0022-328x(03)00780-0

  日期：2003.10

  literature. Ring-opening reactions of the complexes 2–5 with some boron halides (PhBCl2, BCl3, BBr3 and BI3) gave the ferrocene derivatives 7–12, in which the cyclopentadienyl rings bear silyl and boryl groups, respectively. Two of these complexes (9a and 10) were treated with lithium diethylamide in a 1:1 molar ratio, and in both cases selective substitution at the boron atom was observed (13, 14)

  1-Sila- [1] ferrocenophanes（1 - 5）进行了研究相对于它们的NMR光谱参数，特别是涉及的碳原子C中的耦合常数（1）[ 1 Ĵ（13 C（1），13 C（2 ，5）），1 J（29 Si，13 C（1））和1 J（57 Fe，13 C）]]。二硅氧烷6X-射线结构分析表明，含有两个1-sila- [1]二茂铁oph烷单元的具有线性SiOSi基团，与文献中报道的相同化合物的弯曲结构不同。配合物2 – 5与某些卤化硼（PhBCl 2，BCl 3，BBr 3和BI 3）的开环反应得到二茂铁衍生物7 – 12，其中环戊二烯基环分别带有甲硅烷基和硼烷基。这些复合物中的两个（9a和10）在一个1与二乙基氨基锂处理：1的摩尔比，并且在这两种情况下，观察到在硼原子选择性取代（13，14）。所有产物的特征在于它们的1 H-，11 B-，13 C-和29 Si-NMR数据。
• Self-Assembly of Organometallic Block Copolymers:  The Role of Crystallinity of the Core-Forming Polyferrocene Block in the Micellar Morphologies Formed by Poly(ferrocenylsilane-<i>b</i>-dimethylsiloxane) in <i>n</i>-Alkane Solvents
  作者：Jason A. Massey、Karen Temple、Lan Cao、Yahya Rharbi、Jose Raez、Mitchell A. Winnik、Ian Manners

  DOI：10.1021/ja002205d

  日期：2000.11.1

  The organometallic-inorganic diblock copolymer poly(ferrocenyldimethylsilane-b-dimethylsiloxane) (PFDMS-b-PDMS) with a 1:6 block ratio unexpectedly forms:long rodlike micelles rather than spherical structures in a variety of PDMS-selective n-alkane solvents when the solutions are prepared:at. or near ambient; temperature. The cylindrical structures represent the thermodynamically preferred morphology and consist of an iron-rich PFDMS core and a corona of PDMS. The length of the micelles can be varied from 70 nm to 10 mum by altering the method of sample preparation. In addition; the dimensions of the micellar core can be controlled through variations in the length of the PFDMS block,which is achieved by altering the molecular weight of the diblock copolymer while maintaining a constant block ratio. In contrast, when micelles are formed above the T-m of PFDMS (ca. 120-145 degreesC), spherical aggregates are formed, which suggests that crystallization of the core polymer is the driving force for the formation; of wormlike micelles below T-m,. Furthermore, the analogues with amorphous polyferrocene blocks, poly(ferrocenylmethylphenylsilane-b-dimethylsiloxane) (PFMPS-b-PDMS) and poly(ferrocenylmethylethylsilane-b-dimethylsiloxane) (PFMES-b-PDMS), form spherical micelles in hexane at room temperature. This lends further support to the proposition that the crystalline nature of the PFDMS block plays a pivotal role in the unexpected formation of cylindrical micelles. To provide an application of this concept, an analogous PFDMS block copolymer With polyisoprene, PI-b-PFDMS, was prepared and, as predicted, was found to form cylindrical micelles in hexane.
• Stimulus-Responsive Self-Assembly: Reversible, Redox-Controlled Micellization of Polyferrocenylsilane Diblock Copolymers
  作者：Jean-Charles Eloi、David A. Rider、Graeme Cambridge、George R. Whittell、Mitchell A. Winnik、Ian Manners

  DOI：10.1021/ja1105656

  日期：2011.6.15

  In depth studies of the use of electron transfer reactions as a means to control the self-assembly of diblock copolymers with an electroactive metalloblock are reported. Specifically, the redox-triggered self-assembly of a series of polystyrene-block-polyferrocenylsilane (PS-b-PFS) diblock copolymers in dichloromethane solution is described. In the case of the amorphous polystyrene(n)-b-poly(ferrocenylphenylmethylsilane)(m) diblock copolymers (PSn-b-PFMPSm: n = 548, m = 73; n = 71, m = 165; where n and m are the number-averaged degrees of polymerization), spherical micelles with an oxidized PFS core and a PS corona were formed upon oxidation of more than 50% of the ferrocenyl units by [N(C6H4Br-4)(3)][SbX6] (X = Cl, F). Analogous block copolymers containing a poly(ferrocenylethylmethylsilane) (PFEMS) metalloblock, which has a lower glass transition temperature, behaved similarly. However, in contrast, on replacement of the amorphous metallopolymer blocks by semicrystalline poly(ferrocenyldimethylsilane) (PFDMS) segments, a change in the observed morphology was detected with the formation of ribbon-like micelles upon oxidation of PS535-b-PFDMS103 above the same threshold value. Again the coronas consisted of fully solvated PS and the core consisted of partially to fully oxidized PFS associated with the counteranions. When oxidation was performed with [N(C6H4Br-4)(3)] [SbF6], reduction of the cores of the spherical or ribbon-like micelles with [Co(eta-C5Me5)(2)] enabled full recovery of the neutral chains and no significant chain scission was detected.