[(η5-C5H4CO2CH3)Mo(CO)3OTf] | 611175-05-4

• 英文名称: [(η5-C5H4CO2CH3)Mo(CO)3OTf]
• CAS: 611175-05-4
• 化学式: C₁₁H₇F₃MoO₈S
• 分子量: 452.173
• InChiKey: KSKVUGDPYHCAOI-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  (CO)₃(CH₃)Mo(η⁵-C₅H₄COOCH₃) 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 以68%的产率得到[(η5-C5H4CO2CH3)Mo(CO)3OTf]
  参考文献：
  名称：

  Transition metal-catalyzed polymerization of 1,3,5-trioxane

  摘要：

  The molybdenum complexes [(eta(5)-C5Me5)Mo(CO)(3)OTf] (1a), [(eta(5)-C5H5)Mo(CO)(3)X] (2a-2c) (X = F3CSO3 (a), F3CCO2 (b), BF4 (c)), and [(eta(5)-C5H4CO2CH3)Mo(CO)(3)OTf] (3a) catalyze the cationic ring-opening polymerization (ROP) of 1,3,5-trioxane to polyoxymethylene (POM, 5). Hitherto unknown 3a is accessible by treatment of [(eta(5)-C5H4CO2CH3)Mo(CO)(3)CH3] with CF3SO3H. The precipitation time of the polymerization, which is defined in the following as the time until precipitation starts, is dependent on the Lewis acidity of the transition metal center and the presence of formaldehyde or water. 1 3 C-labeled formaldehyde was copolymerized with 1,3,5-trioxane and randomly incorporated into POM. This observation supports the conception that formaldehyde is reversibly formed during the polymerization. Catalyst 2a was successfully applied in the ROP of trioxane even in the presence of up to 3.6 mol% of water. Time-dependent H-1-NMR spectroscopic investigations of the trioxane polymerization revealed the formation of methoxymethyl formate (4) as a by-product, an isomer of trioxane. In the presence of 2a as a catalyst, 4 was degraded to methyl formate (6) and POM (5) in a ratio of about 2:1. This degradation was monitored by H-1-NMR spectroscopy. Catalyst 2a is also able to copolymerize 1,3,5-trioxane with 1,3-dioxepane leading to a thermally stable copolymer after treatment with an aqueous solution of Na2CO3. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00527-8