{(neopentylidene)(2,6-diisopropylphenylimido)((OC(CH3)(CF3)2)2) molybdenum} | 153483-76-2

• 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: {(neopentylidene)(2,6-diisopropylphenylimido)((OC(CH3)(CF3)2)2) molybdenum}
• 英文别名: Mo(N-2,6-i-Pr2C6H3)(CH-t-Bu)(OCMe(CF3)2)2；Mo(CHCMe3)(N-2,6-i-Pr2C6H3)(OCMe(CF3)2)2；[Mo(N-2,6-i-Pr2-C6H3)(CCMe3)(OCMe(CF3)2)2]；2,2-dimethylpropylidene-[2,6-di(propan-2-yl)phenyl]iminomolybdenum(2+);1,1,1,3,3,3-hexafluoro-2-methylpropan-2-olate
• CAS: 153483-76-2
• 化学式: C₂₅H₃₃F₁₂MoNO₂
• 分子量: 703.463
• InChiKey: XOTJCQINXHKWFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.38
• 重原子数：
  41.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  30.82
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  {(neopentylidene)(2,6-diisopropylphenylimido)((OC(CH3)(CF3)2)2) molybdenum} 以 正戊烷 为溶剂， 生成 {(CH(Si(CH3)3)CH2CH(Si(CH3)3))(2,6-diisopropylphenylimido)((OC(CH3)(CF3)2)2) molybdenum}
  参考文献：
  名称：

  钼酰亚胺亚烷基配合物的合成及一些涉及无环烯烃的反应

  摘要：

  Mo(Ct-Bu)(dme)Cl{sub 3} (dme = 1,2-二甲氧基乙烷) 和 Me{sub 3}SiNHAr (Ar = 2,6-二异丙基苯基) 反应生成 Mo(Ct-Bu)( NHAr)Cl{sub 2}(dme) (1)，在用催化量的 NEt{sub 3} 处理后转化为 Mo(CH-t-Bu)(NAr)Cl{sub 2}(dme) ( 2）。Mo(CH-t-Bu)(NAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2}, OCMe{sub 2}(CF{sub 3}) 、Ot-Bu 或 OAr) 已由 2. Mo(Ct-Bu)(NHAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2} 类型的配合物制备，或OAr) 已从 1 制备，但它们不能转化为 Mo(CH-t-Bu)(NAr)(OR){sub 2} 配合物。与

  DOI：

  10.1021/ja00166a023
• 作为产物：
  描述：

  Dichloro-(2,2-dimethylpropylidene)-[2,6-di(propan-2-yl)phenyl]iminomolybdenum 以 乙醚 为溶剂， 生成 {(neopentylidene)(2,6-diisopropylphenylimido)((OC(CH3)(CF3)2)2) molybdenum}
  参考文献：
  名称：

  钼酰亚胺亚烷基配合物的合成及一些涉及无环烯烃的反应

  摘要：

  Mo(Ct-Bu)(dme)Cl{sub 3} (dme = 1,2-二甲氧基乙烷) 和 Me{sub 3}SiNHAr (Ar = 2,6-二异丙基苯基) 反应生成 Mo(Ct-Bu)( NHAr)Cl{sub 2}(dme) (1)，在用催化量的 NEt{sub 3} 处理后转化为 Mo(CH-t-Bu)(NAr)Cl{sub 2}(dme) ( 2）。Mo(CH-t-Bu)(NAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2}, OCMe{sub 2}(CF{sub 3}) 、Ot-Bu 或 OAr) 已由 2. Mo(Ct-Bu)(NHAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2} 类型的配合物制备，或OAr) 已从 1 制备，但它们不能转化为 Mo(CH-t-Bu)(NAr)(OR){sub 2} 配合物。与

  DOI：

  10.1021/ja00166a023

文献信息

• Synthesis of Oligoenes that Contain up to 15 Double Bonds from 1,6-Heptadiynes
  作者：Constantin Czekelius、Jillian Hafer、Zachary J. Tonzetich、Richard R. Schrock、Ronald L. Christensen、Peter Müller

  DOI：10.1021/ja0656705

  日期：2006.12.1

  This paper reports the synthesis of polyene oligomers ("oligoenes") that contain up to 15 double bonds that are identical to the "all five-membered ring" species formed through cyclopolymerization of diisopropyldipropargylmalonate. The oligoenes contain an isopropylidene unit at each end. The isolated oligoenes range from the "dimer" (a pentaene, (E)-di-1,2-[1-(2-methyl-propenyl)-4,4-di-iso-propyl

  本文报道了多烯低聚物（“oligoenes”）的合成，其中包含多达 15 个双键，这些双键与通过二异丙基二炔丙酯的环聚合形成的“所有五元环”物种相同。低聚烯在每端含有一个异亚丙基单元。分离的低聚烯包括“二聚体”（戊烯，(E)-di-1,2-[1-(2-methyl-propenyl)-4,4-di-iso-propyl-carboxy-cyclopent-1-烯基]-乙烯 (3b2)) 到“七聚体”（3b7，十五碳烯）。低聚烯 3b2、3b3、3b4、3b5 和 3b7 是通过醛与适当的单金属 Mo 亚烷基或双金属 Mo 双亚烷基物种（其亚烷基衍生自相同的五元环单体单元）之间的类 Wittig 反应制备的。化合物 3b2、3b4、和 3b6 是通过醛的 McMurry 偶联反应制备的。代表性的醛（“单体”醛）是二异丙基-3-甲酰基-4-（2-甲基丙-1-烯基）环戊-3-烯-1,1-二羧酸酯
• Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts
  作者：Amritanshu Sinha、Richard R. Schrock、Peter Müller、Amir H. Hoveyda

  DOI：10.1021/om060430j

  日期：2006.9.1

  We have found that Mo(NAr)(CHR')(NPh(2))(2) (R' = t-Bu or CMe(2)Ph) and Mo(NAr')(CHCMe(2)Ph)(NPh(2))(2) (Ar = 2,6-i-Pr(2)C(6)H(3); Ar' = 2,6-Me(2)C(6)H(3)) can be prepared through addition of two equivalents of LiNPh(2) to Mo(NR'')(CHR')(OTf)(2)(dme) species (R'' = Ar or Ar' dme = 1,2-dimethoxyethane), although yields are low. A high yield route consists of addition of LiNPh(2) to bishexafluro-t-butoxide

  我们发现 Mo(NAr)(CHR')(NPh(2))(2) (R' = t-Bu or CMe(2)Ph) 和 Mo(NAr')(CHCMe(2)Ph)(NPh (2))(2) (Ar = 2,6-i-Pr(2)C(6)H(3); Ar' = 2,6-Me(2)C(6)H(3)) 可以通过将两当量的 LiNPh(2) 添加到 Mo(NR'')(CHR')(OTf)(2)(dme) 物种（R'' = Ar 或 Ar' dme = 1,2-二甲氧基乙烷）中制备，虽然产量低。高产量路线包括将 LiNPh(2) 添加到双六氟叔丁醇物种中。Mo(NAr)(CHCMe(2)Ph)(NPh(2))(2) 的 X 射线结构表明，两个二苯基酰胺基团的定向方式可以实现 18 个电子计数。二苯基酰胺络合物很容易与 t-BuOH 和 (CF(3))(2)MeCOH 反应，但不容易与空间要求高的双酚 H(2)[Biphen]
• 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
  作者：Harold H. Fox、Jin Kyu Lee、Lee Y. Park、Richard R. Schrock

  DOI：10.1021/om00027a028

  日期：1993.3

  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.
• Ring-Opening Metathesis of a Cyclic Imine
  作者：Gidget K. Cantrell、Steven J. Geib、Tara Y. Meyer

  DOI：10.1021/om000360v

  日期：2000.9.1

  Pyrroline, a five-membered cyclic imine, undergoes ring-opening metathesis with alkylidene complexes of the class Mo(=CHR')(=NAr)(OR)(2) (Ar = 2,6 diisopropylphenyl; R = CMe3, CMe2-(CF3), CMe(CF3)(2); R' = CMe3, CPhMe2). An intermediate pyrroline-bound complex was isolated and characterized crystallographically for the R = CMe2(CF3) derivative. This adduct, Mo(=CHBut)(=NAr)[OCMe2(CF3)](2)[pyrroline], transforms to the mixed bis(imide) product, Mo(=NCH2CH2CH2CH=CHBut)(=NAr)[OMe2(CF3)](2), with a first-order rate constant of 1.4 x 10(-2) min(-1) at 55 degrees C. The reaction of the R = CMe3 derivative produces not only the ring-opened product but also a byproduct, Mo[CH(CMe2Ph)(C4H8N)](=O)(=NAr)(OBut).
• Reduction of molybdenum imido-alkylidene complexes in the presence of olefins to give molybdenum(IV) complexes
  作者：Jennifer Robbins、Guillermo C. Bazan、John S. Murdzek、Marie B. O'Regan、Richard R. Schrock

  DOI：10.1021/om00054a068

  日期：1991.8

  Mo(CH-t-Bu)(NAr)[OCMe(CF3)2]2 (1a) (Ar = 2,6-diisopropylphenyl) reacts with excess vinyltrimethylsilane to give Mo(NAr)[OCMe(CF3)2]2(CH2 = CHSiMe3) (2). Complex 2 reacts with trimethylphosphine, 2-butyne, and excess ethylene to give Mo(NAr)[OCMe(CF3)2]2(PMe3)2 (3), Mo(NAr)[OCMe(CF3)2]2(MeC = CMe) (4), or Mo(NAr)[OCMe(CF3)2]2(C4H8) (8), respectively. Complex 4 reacts with PMe3 to give Mo(NAr)[OCMe(CF3)2]2(MeC = CMe)(PMe3) (5), and 8 reacts with PMe3 to give Mo(NAr)(OCMe(CF3)2]2(CH2 = CH2)(PMe3) (9). Metallacycle Mo(CH2CH2CH2)(NAr)[OCMe(CF3)2]2 (6) decomposes in the presence of excess ethylene to form 8 and reacts with trimethylphosphine to give Mo(CH2)(NAr)[OCMe(CF3)2]2(PMe3) (7). Mo(CH-t-Bu)(NAr)(O-t-Bu)2 (1b) reacts with excess ethylene to give Mo(CH2CH2CH2)(NAr)(O-t-Bu)2 (10), which reacts with trimethylphosphine to give Mo(CH2)(NAr)(O-t-Bu)2(PMe3) (11). 10 decomposes to [Mo(NAr)(O-t-Bu)2]2 (12; C2/c, a = 14.772 (6) angstrom, b = 15.470 (4) angstrom, c = 10.625 (8) angstrom, beta = 104.62 (3)-degrees, Z = 4, M(r) = 834.88, rho = 1.276 g/cm3, mu = 5.99 cm-1, R1 = 0.035, R2 = 0.047). 12 is an imido-bridged dimer that is believed to form upon coupling of methylene ligands in two Mo(NAr)(CH2)(O-t-Bu)2 complexes.