Mo(2,6-dimethylphenylimido)2(CH2CMe2Ph)2 | 153842-49-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Mo(2,6-dimethylphenylimido)2(CH2CMe2Ph)2
• 英文别名: Mo(NAr_Me)₂(CH₂CMe₂Ph)₂；Mo(2,6-dimethylphenylimido)₂(CH₂CMe₂Ph)₂
• CAS: 153842-49-0
• 化学式: C₃₆H₄₄MoN₂
• 分子量: 600.699
• InChiKey: HZRQQSBWHRIERS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.2
• 重原子数：
  39.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  24.72
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  Mo(2,6-dimethylphenylimido)2(CH2CMe2Ph)2 、 在 二苯胺盐酸盐 作用下， 以 苯 为溶剂， 反应 7.0h， 以26.8%的产率得到
  参考文献：
  名称：

  含2-吡啶基取代的苯氧化物配体的钼和钨亚烷基络合物

  摘要：

  In the interest of preparing molybdenum and tungsten alkylidene complexes for olefin metathesis that are longer-lived at high temperatures (similar to 150 degrees C or above), we synthesized complexes that contain a phenoxide ligand with a 2-pyridyl in one ortho position and a mesityl (Mes) or 2,4,6-i-Pr3C6H2 (Trip) in the other ortho position ([MesON](-) or [TripON](-), respectively). The alkylidene (neophylidene) complexes that were prepared include W(O)(CHCMe2Ph)(Me(2)Pyr)(RON) (R = Mes or Trip), Mo(NC6F5)(CHCMe2Ph)(RON)Cl, Mo(N-2,6- Me2C6H3)(CHCMe2Ph)(RON)Cl, Mo(N-t-Bu)(CHCMe2Ph)(RON)Cl, and M(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(TripON)(OTf) (M = Mo or W). The reaction between Mo(NAr)(CHCMe2Ph)(TripON)(OTf) and ethylene yielded an ethylene complex, Mo(NAr)(C2H4)(TripON)(OTf)(ether). All neophylidene complexes were essentially unreactive toward terminal olefins at 22 degrees C and showed modest homocoupling activity (at 80 or 100 degrees C) and alkane metathesis activity (at 150 and 200 degrees C). W(O)(CHCMe2Ph)(Me(2)Pyr)(MesON) also stereoselectively polymerized several substituted norbornadienes at 100 degrees C.

  DOI：

  10.1021/acs.organomet.6b00644
• 作为产物：
  描述：

  [Mo(N-2,6-Me2C6H3)2Cl2(dimethoxyethane)] 、 2-甲基-2-苯基丙基氯化镁 以 乙醚 为溶剂， 以82%的产率得到Mo(2,6-dimethylphenylimido)2(CH2CMe2Ph)2
  参考文献：
  名称：

  Ligand variation in alkylidene complexes of the type Mo(CHR)(NR′)(OR″)2

  摘要：

  A variety of complexes of the type Mo(NR)2Cl2L2 (R = 4-Br-2,6-(i)Pr2-C6H2, 4-CN-2,6-(i)Pr2-C6H2, 3,5-Me2-C6H3, 2-(i)Pr-C6H4, 2-CF3-C6H4, 2-Ph-C6H4, and 1-adamantyl; L = 1/2 DME or pyridine) have been synthesized by treating [NH4]2[Mo2O7] with four equivalents of RNH2 in the presence of Me3SiCl and Et3N. They are readily alkylated by Grignard reagents to give complexes of the type Mo(NR)2(CH2R')2 (R=4-Br-2,6-(i)Pr2-C6H2, 4-CN-2,6-(i)Pr2-C6H2, 2,6-Me2-C6H3, 3,5-Me2-C6H3, 2-(t)Bu-C6H4, 2-(i)Pr-C6H4, 2-CF3-C6H4, 2-Ph-C6H4, 1-adamantyl, R'= (t)Bu or PhMe2C) from which alkylidene complexes of the type Mo(NR)(CHR')(OTf)2(DME) are formed upon addition of triflic acid. Addition of various alkoxides to the triflate complexes yields four-coordinate complexes of the type Mo(NR)(CHR')(OR')2 (combinations include R = 2,6-(i)Pr2-C6 H 3, 4-Br-2,6-(i)Pr2-C6H2, 4-CN-2,6-(i)Pr2-C6H2, 2,6-Me2-C6H3, 3,5-Me2-C6H3, 2-Bu-C6H4, 2-(i)Pr-C6H4, 2-CF3-C6H4, 2-Ph-C6H4, and 1-adamantyl; OR'' = OCMe3, OCEt3, 0-1-adamantyl, OCHMe2, OCMe2(CF3), OCMe(CF3)2, OC(CF3)3, and OC(CF3)2CF2CF2CF3).

  DOI：

  10.1016/0022-328x(93)86071-o

文献信息

• Understanding Synthetic Peculiarities of Cationic Molybdenum(VI) Imido Alkylidene N‐Heterocyclic Carbene Complexes
  作者：Roman Schowner、Wolfgang Frey、Michael R. Buchmeiser

  DOI：10.1002/ejic.201900021

  日期：2019.4.16

  novel synthetic approaches to molybdenum imido alkylidene N‐heterocyclic carbene (NHC) complexes including the first NHC alkylidene complexes featuring pentafluorophenyl‐substituted imido ligands, highly basic 6‐Mes (6‐Mes = 1,3‐dimesityl‐3,4,5,6‐tetrahydropyrimidin‐2‐ylidene) NHC ligands and the preparation of the first representatives of cationic 14‐electron Mo imido alkylidene NHC catalysts bearing

  我们报告了一种新的合成方法，用于合成亚氨基钼亚烷基N-杂环卡宾（NHC）配合物，包括首个以五氟苯基取代的亚氨基配体为特征的NHC亚烷基配合物，高度碱性的6-MES（6-MES = 1,3-diMESityl-3,4 ，5,6-四氢嘧啶-2-亚丙基）NHC配体和带有空间要求的阴离子三苯醚配体的阳离子14-电子钼亚氨基亚烷基NHC催化剂的首批制备。同样，Mo亚氨基亚烷基和亚烷基NHC双醇盐配合物[Mo（NR）（CHCME 2 Ph）（NHC）（OR'）2 ]，[Mo（NH-C 6 F 5）（CCME 2 Ph）（a IMES） OCME（CF 3）2 } 2]（一IMES = 1,3- diMESitylimidazol -5-亚基，异常Ç 5结合的imidazolylidene）和[沫（NH-2-CF 3 -C 6 H ^ 4）（CCME 2 PH）（6-MES）给出了OCME（CF 3）2