Mo(N-2,6-Pr(i)2C6H3)2(CH2Ph)2 | 147283-00-9

• 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(N-2,6-Pr(i)2C6H3)2(CH2Ph)2
• CAS: 147283-00-9
• 化学式: C₃₈H₄₈MoN₂
• 分子量: 628.753
• InChiKey: SPLJYODTJPAVMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.06
• 重原子数：
  41.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  乙二醇二甲醚 、 Mo(N-2,6-Pr(i)2C6H3)2(CH2Ph)2 、 三氟甲磺酸 以 乙二醇二甲醚 为溶剂， 以55%的产率得到
  参考文献：
  名称：

  Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents

  摘要：

  Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe2Ph)(NAr)(ORF6)2 (1a) or Mo(CHCMe3)(NAr)(ORF6)2 (1b) in pentane (ORF6 = OCMe(CF3)2) yielded crystalline, red-orange anti-Mo[CHCH2CH(OMe)CH2CH3](NAr)(ORF6)2 (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(ORF6)2Mo=CHCH2CH(OMe)]2C6H4(3). Styrene reacts with la or lb in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(ORF6)2(DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethoxystyrene react analogously to yield dark red syn-Mo(CH-4-C6H4-NMe2)(NAr)(ORF6)2 (DME) (5) and red anti-Mo[CH-2,4,6-C6H2-(OMe)3](NAr)(ORF6)2(DME) (6). 4 also can be synthesized from Mo(NAr)2Cl2(DME) via Mo(NAr)2(CH2Ph)2 and Mo(CHPh)(NAr)(OTf)2(DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(RF60)2(ArN)Mo(CH)6-Mo(NAr)(ORF6)2(DME) (9a). A related complex, syn-(Et2O)(RF60)2(ArN)Mo(CH)6Mo(NAr)-(ORF6)2(Et2O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(RF60)2(ArN)Mo(CH)6Mo(NAr)(ORF6)2(THF) (9c) was observed upon dissolving 9a in THF. Addition of 4 equiv of LiO-t-Bu and 2 equiv of quinuclidine (quin) to 9a yields metallic green (quin)(t-BuO)2(ArN)Mo(CH)6Mo(NAr)(0-t-Bu)2(quin) (9d). 1,4-Divinylbenzene reacts smoothly with la or lb to give another conjugated difunctional alkylidene complex, 1,4-[(DME)(RF60)2(ArN)MoCH]2C6H4 (10a). Mo(CH2)(NAr)(ORF6)2(DME) (11a) could be generated and observed by H-1 NMR upon adding an excess of ethylene to a solution of lb in DME-d10 in a septum-sealed NMR tube. Addition of 2,2'-bipyridine (bpy) to 11a yielded isolable Mo(CH2)(NAr)(ORF6)2(bpy) (11b). 2,3-Dicarbomethoxynorbornadiene (100 equiv) could be polymerized in a living manner in DME using lb, 4, 5, 9a, 9b, or 10a as the initiator. 2,3-Bis(trifluoromethyl)norbomadiene (100 equiv) was also polymerized in a living manner by la in DME. Addition of an excess of LiO-t-Bu (8 equiv) to a solution of 3 in toluene, followed by 200 equiv of methyltetracyclododecene (MTD), gave low-polydispersity poly-MTD (M(W)/M(n) = 1.03) in 93% yield. Complexes 4,5,9a, 9b, and 10a react cleanly with pivaldehyde or benzaldehyde in CD2Cl2 or DME. A combination of Wittig reactions was used to prepare the di-tert-butyl-capped polyenes(t-Bu)(CH=CH)n(t-Bu)(n=4,6,8). The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer.

  DOI：

  10.1021/om00027a028
• 作为产物：
  描述：

  benzyl potassium 、 二氯双[（2,6-二异丙基苯基）亚氨基]（1,2-二甲氧基乙烷）钼（VI） 以 四氢呋喃 、 乙醚 为溶剂， 以76%的产率得到Mo(N-2,6-Pr(i)2C6H3)2(CH2Ph)2
  参考文献：
  名称：

  Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents

  摘要：

  Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe2Ph)(NAr)(ORF6)2 (1a) or Mo(CHCMe3)(NAr)(ORF6)2 (1b) in pentane (ORF6 = OCMe(CF3)2) yielded crystalline, red-orange anti-Mo[CHCH2CH(OMe)CH2CH3](NAr)(ORF6)2 (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(ORF6)2Mo=CHCH2CH(OMe)]2C6H4(3). Styrene reacts with la or lb in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(ORF6)2(DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethoxystyrene react analogously to yield dark red syn-Mo(CH-4-C6H4-NMe2)(NAr)(ORF6)2 (DME) (5) and red anti-Mo[CH-2,4,6-C6H2-(OMe)3](NAr)(ORF6)2(DME) (6). 4 also can be synthesized from Mo(NAr)2Cl2(DME) via Mo(NAr)2(CH2Ph)2 and Mo(CHPh)(NAr)(OTf)2(DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(RF60)2(ArN)Mo(CH)6-Mo(NAr)(ORF6)2(DME) (9a). A related complex, syn-(Et2O)(RF60)2(ArN)Mo(CH)6Mo(NAr)-(ORF6)2(Et2O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(RF60)2(ArN)Mo(CH)6Mo(NAr)(ORF6)2(THF) (9c) was observed upon dissolving 9a in THF. Addition of 4 equiv of LiO-t-Bu and 2 equiv of quinuclidine (quin) to 9a yields metallic green (quin)(t-BuO)2(ArN)Mo(CH)6Mo(NAr)(0-t-Bu)2(quin) (9d). 1,4-Divinylbenzene reacts smoothly with la or lb to give another conjugated difunctional alkylidene complex, 1,4-[(DME)(RF60)2(ArN)MoCH]2C6H4 (10a). Mo(CH2)(NAr)(ORF6)2(DME) (11a) could be generated and observed by H-1 NMR upon adding an excess of ethylene to a solution of lb in DME-d10 in a septum-sealed NMR tube. Addition of 2,2'-bipyridine (bpy) to 11a yielded isolable Mo(CH2)(NAr)(ORF6)2(bpy) (11b). 2,3-Dicarbomethoxynorbornadiene (100 equiv) could be polymerized in a living manner in DME using lb, 4, 5, 9a, 9b, or 10a as the initiator. 2,3-Bis(trifluoromethyl)norbomadiene (100 equiv) was also polymerized in a living manner by la in DME. Addition of an excess of LiO-t-Bu (8 equiv) to a solution of 3 in toluene, followed by 200 equiv of methyltetracyclododecene (MTD), gave low-polydispersity poly-MTD (M(W)/M(n) = 1.03) in 93% yield. Complexes 4,5,9a, 9b, and 10a react cleanly with pivaldehyde or benzaldehyde in CD2Cl2 or DME. A combination of Wittig reactions was used to prepare the di-tert-butyl-capped polyenes(t-Bu)(CH=CH)n(t-Bu)(n=4,6,8). The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer.

  DOI：

  10.1021/om00027a028

文献信息

• Transition metal imido catalysts for ethylene polymerisation
  作者：Martyn P Coles、Christopher I Dalby、Vernon C Gibson、Ian R Little、Edward L Marshall、M.Helena Ribeiro da Costa、Sergio Mastroianni

  DOI：10.1016/s0022-328x(99)00452-0

  日期：1999.12

  appropriate alkylating reagents and investigated as precursors to well-defined cationic alkyl catalysts. Treatment of (5) with [Ph3C][B(C6F5)4] affords the cationic η2-benzyl species [Cr(N-tBu)2(η2-CH2Ph)][B(C6F5)4] (12) while its reaction with [PhNMe2H][B(C6F5)4] liberates toluene to give a mixture of the mono and bis(dimethylaniline) adducts [Cr(N-tBu)2(η2-CH2Ph)(NMe2Ph)][B(C6F5)4] (14) and [Cr(N-tB

  亚胺基络合物CpV（N-2-MeC 6 H 4）Cl 2（1），Cr（N- t Bu）2 Cl 2（2），CpNb（N-2- t BuC 6 H 4）Cl 2（3）和Mo（N- t Bu）2 Cl 2（4）已被测试与二乙基铝氯化物或甲基铝氧烷（MAO）助催化剂结合用于乙烯聚合的前催化剂。钒的前体具有最高的活性，但寿命短，而铬系则具有中等活性的长寿命催化剂。在所有测试条件下，铌和钼衍生物的活性相对较低。由钒和铬催化剂产生的聚乙烯具有高分子量，几乎没有支链。二烷基络合物Cr（N- t Bu）2（CH 2 Ph）2（5），Cr（N-2,6-Pr i 2 C 6 H 3）2（CH2 Ph）2（6），Cr（N-2,6-Pr i 2 C 6 H 3）2 Me 2（7），Mo（N- t Bu）2（CH 2 Ph）2（8），Mo （N-2,6-Pr i 2 C 6 H 3）2（CH 2 Ph）2（9），（C