| 1085283-54-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 1085283-54-0
• 化学式: C₄₄H₆₂N₄O₄S₂Zn₂
• 分子量: 905.913
• InChiKey: WTCRTJHTJLSROH-USYLWMMOSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• 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

• 作为产物：
  描述：

  2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(meta-phenylene) 以 正己烷 、 甲苯 、 苯 为溶剂， 生成
  参考文献：
  名称：

  Bimetallic Calcium and Zinc Complexes with Bridged β-Diketiminate Ligands: Investigations on Epoxide/CO₂ Copolymerization

  摘要：

  A series of dinucleating bis(beta-diketiminate) ligands with rigid bridges has been prepared. In all cases the beta-diketiminate unit is 2,6-iPr(2)C(6)H(3)NC(Me)C(H)C(Me)N-(bridge), and the bridges are either paraphenylene, meta-phenylene or 2, 6-pyridylene (the dinucleating ligands are abbreviated as PARA-H-2,H- META-H-2 and PYR-H-2, respectively). These ligands have been converted to heteroleptic bimetallic calcium and zinc complexes. For calcium, only the PARA-phenylene bridged ligand led to a heteroleptic bimetallic calcium amide complex PARA-[CaN(SiMe3)(2) center dot THF](2). For the other ligands, homoleptic complexes have been isolated: META-Ca and PYR-Ca. For zinc, the whole range of heteroleptic amides could be isolated: PARA-[ZnN(SiMe3)(2)](2), META-[ZnN(SiMe3)(2)](2), and PYR-[ZnN(SiMe3)(2)](2). Analogue ethylzinc complexes have been prepared in quantitative yields: PARA-(ZnEt)(2), META-(ZnEt)(2), and PYR-(ZnEt)(2). Reactions of the ethylzinc complexes with SO2 gave access to the ethylsulfinate complexes META-(ZnO2SEt)(2) and PYR-(ZnO2SEt)(2); for the parci-phenylene bridged ligand no products could be isolated. Crystal structures of the following complexes are presented: (META-Ca)(2), PARA-[CaN(SiMe3)(2) center dot THF](2), PARA[ZnN(SiMe3)(2), META-[ZnN(SiMe3)(2)](2), PYR-(ZnEt)(2), and PYR-(ZnO2SEt)(2). All heteroleptic complexes have been tested for activity in the copolymerization of cyclohexene oxide (CHO) and CO,. The bimetallic complex PARA-[CaN(SiMe3)(2)-THF](2) is not active. For zinc, the PARA and META complexes were found to be active under highly concentrated conditions (Zn/CHO ratio of 1/1000; no solvent), but no significant polymer yields could be achieved with PYR complexes. This is either due to conformational changes of the complex or to coordination of the pyridylene N atom to the catalytic centers. The order of activity found in the bimetallic zinc complexes is META > PARA. This is likely due to a more advantageous Zri center dot center dot center dot Zn distance in the meta-phenylene bridged bimetallic catalysts. There are several indications for bimetallic action. First of all, the ethylzinc systems PARA-(ZnEt)(2) and META-(ZnEt)(2) initiate CHO/CO2 copolymerization, whereas monometallic ethylzinc catalysts are not reactive. Second, the bimetallic zinc catalysts are also highly active under diluted conditions: a low metal/CHO ratio of 1/3000 gave high-MW polyiners (M-n > 100.000, PDI = 1.33) with essentially only carbonate linkages. In contrast, monometallic systems show a drastic loss of activity upon dilution. Finally, the bimetallic catalyst META-[ZnN(SiMe3)212 shows a significantly higher activity than a comparable monometallic model system.

  DOI：

  10.1021/om800597f