rac-[(SBI)Zr(CH2SiMe2C6H4NMe2)][MeB(C6F5)3] | 1252003-68-1

• 英文名称: rac-[(SBI)Zr(CH2SiMe2C6H4NMe2)][MeB(C6F5)3]
• CAS: 1252003-68-1
• 化学式: C₁₁H₁₈NSi*C₁₉H₃BF₁₅*C₂₀H₁₈Si*Zr
• 分子量: 1097.05
• InChiKey: BLUXLAPAGACDBP-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-己烯 、 rac-[(SBI)Zr(CH2SiMe2C6H4NMe2)][MeB(C6F5)3] 以 氘代甲苯 为溶剂， 生成 rac-[(SBI)Zr((CH2CH(Bu))(n)CH2SiMe2C6H4NMe2)(MeB(C6F5)3)]
  参考文献：
  名称：

  GPC and ESI-MS Analysis of Labeled Poly(1-Hexene): Rapid Determination of Initiated Site Counts during Catalytic Alkene Polymerization Reactions

  摘要：

  Accurate active-site counts are necessary for the establishment of olefin polymerization kinetics, yet current techniques are often tedious and limited in sensitivity. Herein, we describe the development of a novel method for determining the fraction of initiated catalyst using standard gel-permeation chromatography (GPC). The first insertion of monomer into the chromophore-bearing zirconocene 1 generates a single equivalent of a labeled polymer chain. The polymer-bound label can be quantified as a function of polymer molecular weight using a GPC with a UV detector; simultaneous RI detection allows both the extent of monomer conversion and the molecular-weight distribution to also be established. We estimate that monomer to catalyst ratios of as high as 10 000:1 can be measured using this technique.

  DOI：

  10.1021/ja105775r
• 作为产物：
  描述：

  rac-[(SBI)Zr(Me)(dimethylanilinyldimethylsilylmethyl)] 、 三(五氟苯基)硼烷 以 氘代甲苯 为溶剂， 生成 rac-[(SBI)Zr(CH2SiMe2C6H4NMe2)][MeB(C6F5)3]
  参考文献：
  名称：

  GPC and ESI-MS Analysis of Labeled Poly(1-Hexene): Rapid Determination of Initiated Site Counts during Catalytic Alkene Polymerization Reactions

  摘要：

  Accurate active-site counts are necessary for the establishment of olefin polymerization kinetics, yet current techniques are often tedious and limited in sensitivity. Herein, we describe the development of a novel method for determining the fraction of initiated catalyst using standard gel-permeation chromatography (GPC). The first insertion of monomer into the chromophore-bearing zirconocene 1 generates a single equivalent of a labeled polymer chain. The polymer-bound label can be quantified as a function of polymer molecular weight using a GPC with a UV detector; simultaneous RI detection allows both the extent of monomer conversion and the molecular-weight distribution to also be established. We estimate that monomer to catalyst ratios of as high as 10 000:1 can be measured using this technique.

  DOI：

  10.1021/ja105775r

文献信息

• Mechanistic Investigations into the Behavior of a Labeled Zirconocene Polymerization Catalyst
  作者：Beth M. Moscato、Bolin Zhu、Clark R. Landis

  DOI：10.1021/om3000955

  日期：2012.3.12

  Kinetics associated with the [(SBI)Zr(CH2SiMe2(C6H4)NMe2)][MeB(C6F5)(3)] (1a)-catalyzed polymerization of 1-hexene in a mixed toluene-d(8)/chlorobenzene-d(5) solvent at -33 degrees C were investigated via H-1 NMR and compared to the kinetics associated with the (SBI)ZrMe(MeB(C6F5)(3)) (1c)-catalyzed polymerization of 1-hexene under identical conditions. In the presence of 1-hexene, both catalysts form an identical propagating species, (SBI)Zr(poly-1-hexyl)(MeB(C6F5)(3)) (1b), but the concentration of 1b during 1a-catalyzed polymerization is only ca. 40% of the anticipated value. Under reaction conditions, 1b reacts reversibly with the model complex p-TMS-C6H4-NMe2 (2) to yield the outer-sphere ion pair tentatively identified as [(SBI)Zr(poly-1-hexyl)(2)][MeB(C6F5)(3)] (1e), which acts as art essentially dormant site during 1-hexene polymerization. Warming of 1b in the absence of additives generates the well-defined hydridoborate complex (SBI)ZrMe(HB(C6F5)(3)) (1d), which does not reinitiate in the presence of 1-hexene. beta-Hydride elimination of 1b in the presence of additives such as 1,2-dichloroethane and 2 results in catalyst decomposition.