(4-MeO-C6H4C)W(OC(CF3)2Me)3(DME) | 1034311-49-3

• 英文名称: (4-MeO-C6H4C)W(OC(CF3)2Me)3(DME)
• 英文别名: W(≡CC₆H₄OMe)(OC(CF₃)₂Me)₃(DME)
• CAS: 1034311-49-3
• 化学式: C₂₄H₂₆F₁₈O₆W
• 分子量: 936.288
• InChiKey: UUKKOECZYLXVAJ-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：

  3-己炔 、 (4-MeO-C6H4C)W(OC(CF3)2Me)3(DME) 以 not given 为溶剂， 生成 W(CEt)[OCMe(CF3)2]3(1,2-dimethoxyethane)
  参考文献：
  名称：

  Synthetic, Mechanistic, and Computational Investigations of Nitrile-Alkyne Cross-Metathesis

  摘要：

  The terminal nitride complexes NW(OC(CF3)(2)Me)(3)(DME) (1-DME), [Li(DME)(2)][NW(OC(CF3)(2)Me)(4)] (2), and [NW(OCMe2CF3)(3)](3) (3) were prepared in good yield by salt elimination from [NWCl3](4). X-ray structures revealed that 1-DME and 2 are monomeric in the solid state. All three complexes catalyze the cross-metathesis of 3-hexyne with assorted nitriles to form propionitrile and the corresponding alkyne. Propylidyne and substituted benzylidyne complexes RCW(OC(CF3)(2)Me)(3) were isolated in good yield upon reaction of 1-DME with 3-hexyne or 1-aryl-1-butyne. The corresponding reactions failed for 3. Instead, EtCW(OC(CF3)Me-2)(3) (6) was prepared via the reaction of W-2(OC(CF3)Me-2)(6) with 3-hexyne at 95 degrees C. Benzylidyne complexes of the form ArCW(OC(CF3)Me-2)(3) (Ar = aryl) then were prepared by treatment of 6 with the appropriate symmetrical alkyne ArCCAr. Three coupled cycles for the interconversion of 1-DME with the corresponding propylidyne and benzylidyne complexes via [2 + 2] cycloaddition-cycloreversion were examined for reversibility. Stoichiometric reactions revealed that both nitrile-alkyne cross-metathesis (NACM) cycles as well as the alkyne cross-metathesis (ACM) cycle operated reversibly in this system. With catalyst 3, depending on the aryl group used, at least one step in one of the NACM cycles was irreversible. In general, catalyst 1-DME afforded more rapid reaction than did 3 under comparable conditions. However, 3 displayed a slightly improved tolerance of polar functional groups than did 1-DME. For both 11-DME and 3, ACM is more rapid than NACM under typical conditions. Alkyne polymerization (AP) is a competing reaction with both 1-DME and 3. It can be suppressed but not entirely eliminated via manipulation of the catalyst concentration. As AP selectively removes 3-hexyne from the system, tandem NACM-ACM-AP can be used to prepare symmetrically substituted alkynes with good selectivity, including an arylene-ethynylene macrocycle. Alternatively, unsymmetrical alkynes of the form EtCCR (R variable) can be prepared with good selectivity via the reaction of RCN with excess 3-hexyne under conditions that suppress AP. DFT calculations support a [2 + 2) cycloaddition-cycloreversion mechanism analogous to that of alkyne metathesis. The barrier to azametalacyciobutadiene ring formation/breakup is greater than that for the corresponding metalacyclobutadiene. Two distinct high-energy azametalacyclobutadiene intermediates were found. These adopted a distorted square pyramidal geometry with significant bond localization.

  DOI：

  10.1021/ja800020w
• 作为产物：
  描述：

  W(CEt)[OCMe(CF3)2]3(1,2-dimethoxyethane) 、 1-(1-丁炔-1-基)-4-甲氧基苯 以 not given 为溶剂， 生成 (4-MeO-C6H4C)W(OC(CF3)2Me)3(DME)
  参考文献：
  名称：

  Synthetic, Mechanistic, and Computational Investigations of Nitrile-Alkyne Cross-Metathesis

  摘要：

  The terminal nitride complexes NW(OC(CF3)(2)Me)(3)(DME) (1-DME), [Li(DME)(2)][NW(OC(CF3)(2)Me)(4)] (2), and [NW(OCMe2CF3)(3)](3) (3) were prepared in good yield by salt elimination from [NWCl3](4). X-ray structures revealed that 1-DME and 2 are monomeric in the solid state. All three complexes catalyze the cross-metathesis of 3-hexyne with assorted nitriles to form propionitrile and the corresponding alkyne. Propylidyne and substituted benzylidyne complexes RCW(OC(CF3)(2)Me)(3) were isolated in good yield upon reaction of 1-DME with 3-hexyne or 1-aryl-1-butyne. The corresponding reactions failed for 3. Instead, EtCW(OC(CF3)Me-2)(3) (6) was prepared via the reaction of W-2(OC(CF3)Me-2)(6) with 3-hexyne at 95 degrees C. Benzylidyne complexes of the form ArCW(OC(CF3)Me-2)(3) (Ar = aryl) then were prepared by treatment of 6 with the appropriate symmetrical alkyne ArCCAr. Three coupled cycles for the interconversion of 1-DME with the corresponding propylidyne and benzylidyne complexes via [2 + 2] cycloaddition-cycloreversion were examined for reversibility. Stoichiometric reactions revealed that both nitrile-alkyne cross-metathesis (NACM) cycles as well as the alkyne cross-metathesis (ACM) cycle operated reversibly in this system. With catalyst 3, depending on the aryl group used, at least one step in one of the NACM cycles was irreversible. In general, catalyst 1-DME afforded more rapid reaction than did 3 under comparable conditions. However, 3 displayed a slightly improved tolerance of polar functional groups than did 1-DME. For both 11-DME and 3, ACM is more rapid than NACM under typical conditions. Alkyne polymerization (AP) is a competing reaction with both 1-DME and 3. It can be suppressed but not entirely eliminated via manipulation of the catalyst concentration. As AP selectively removes 3-hexyne from the system, tandem NACM-ACM-AP can be used to prepare symmetrically substituted alkynes with good selectivity, including an arylene-ethynylene macrocycle. Alternatively, unsymmetrical alkynes of the form EtCCR (R variable) can be prepared with good selectivity via the reaction of RCN with excess 3-hexyne under conditions that suppress AP. DFT calculations support a [2 + 2) cycloaddition-cycloreversion mechanism analogous to that of alkyne metathesis. The barrier to azametalacyciobutadiene ring formation/breakup is greater than that for the corresponding metalacyclobutadiene. Two distinct high-energy azametalacyclobutadiene intermediates were found. These adopted a distorted square pyramidal geometry with significant bond localization.

  DOI：

  10.1021/ja800020w

文献信息

• Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate <i>N</i>-Heterocyclic Carbenes
  作者：Iris Elser、Jonas Groos、Philipp M. Hauser、Maximilian Koy、Melita van der Ende、Dongren Wang、Wolfgang Frey、Klaus Wurst、Jan Meisner、Felix Ziegler、Johannes Kästner、Michael R. Buchmeiser

  DOI：10.1021/acs.organomet.9b00481

  日期：2019.11.11

  molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic

  已经合成了带有单齿，双齿和三齿N-杂环卡宾（NHC）的新型钨和钼亚烷基络合物。在络合物前所未有结构的形成轴承ñ -叔丁基取代基的咪唑（在）观察-2-亚基，导致含有异常卡宾钼络合物（钼-4）和桥接O，C，C-钳配体（Mo-10）和含有阳离子咪唑啉鎓标记的醇盐的钨络合物（W-5），所述醇盐与阴离子钨中心形成内盐。无论是异常卡宾在结合的Mo-4和O，C，的C-钳型结构的Mo-10X射线单晶X射线分析证实了W-5的结构，W-4合成过程中形成的次要副产物（W-8）的单晶X射线结构支撑了W-5的结构。，显示出上述的内部盐状结构。还研究了新型亚烷基配合物在1-苯基-1-丙炔炔复分解过程中形成具有弱配位阴离子（WCA）的先前假定的准阳离子物种的能力。总体而言，掺入二齿和强σ捐赠的NHC以及引入更好的离去基团并没有导致预期的催化活性增加。尽管配体球相同，但从钼变为钨会导致双齿体系的活性完全丧失。
• Cationic Tungsten Alkylidyne <i>N</i> ‐Heterocyclic Carbene Complexes: Synthesis and Reactivity in Alkyne Metathesis
  作者：Philipp M. Hauser、Melita Ende、Jonas Groos、Wolfgang Frey、Dongren Wang、Michael R. Buchmeiser

  DOI：10.1002/ejic.202000503

  日期：2020.8.31

  The first cationic and neutral tungsten alkylidyne N‐heterocyclic carbene (NHC) complexes bearing one triflate ligand were synthesized and tested for their reactivity in alkyne metathesis. Both types of tungsten alkylidyne complexes display a higher productivity in alkyne metathesis than the analogous neutral tungsten alkylidyne NHC trisalkoxide complexes. Reaction of W(≡CC6H4OMe)(1,3‐bis(1‐hydroxy‐1

  合成了第一个带有一个三氟甲磺酸酯配体的阳离子和中性钨亚烷基钨N杂环卡宾（NHC）配合物，并测试了它们在炔烃复分解中的反应性。两种类型的钨亚烷基钨配合物在炔烃复分解中均比类似的中性钨亚烷基钨NHC三烷氧化物配合物显示出更高的生产率。W（≡CC的反应6 ħ 4 OME）（1,3-双（1-羟基-1,1-二三氟甲基乙基） -咪唑烷-2-亚基）氯（W18）用的AgB（AR ˚F）4（AR ˚F =据我们所知，3,5-双（三氟甲基）苯基）意外地形成了第一个阳离子双钨酸正己二烯W 2（1,3-双（1-羟基-1,1-三氟甲基乙基）-咪唑-2-亚基）2（MeCN）（µ -（（Ar）CC（Ar）））+（B（Ar F）4）–（W19，Ar = C 6 H 4 OMe），这表明双分子分解是阳离子钨亚烷基NHC复合物的可能分解途径。阳离子钨次烷基的反应NHC络合物W（≡CC 6 ħ 4 OME）（1,3- diisopropylimidazol