{(2-methyl-2-phenyl-propylidene)((2,6-dimethylphenyl)imido)molybdenum(VI)bis(hexafluoro-tert-butoxide)} | 153414-47-2

• 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: {(2-methyl-2-phenyl-propylidene)((2,6-dimethylphenyl)imido)molybdenum(VI)bis(hexafluoro-tert-butoxide)}
• 英文别名: Mo(CHCMe₂Ph)(N-2,6-Me₂C₆H₃)[OCMe(CF₃)₂]₂；Mo(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂；Mo(CHCMe2Ph)(N-2,6-Me2C6H3)[OC(CH3)(CF3)2]2；Mo(CHCMe2Ph)(N-2,6-Me2C6H3)[OCCH3(CF3)2]2；Mo(CHCMe2Ph)(N-2,6-Me2C6H3)(OCMe(CF3)2)2；Mo(N-2,6-Me2C6H3)(CHCMe2Ph)[OCMe(CF3)2]2
• CAS: 153414-47-2；153483-72-8；154002-56-9
• 化学式: C₂₆H₂₇F₁₂MoNO₂
• 分子量: 709.427
• InChiKey: ZDENNICPDOKBLW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.68
• 重原子数：
  42.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  {(2-methyl-2-phenyl-propylidene)((2,6-dimethylphenyl)imido)molybdenum(VI)bis(hexafluoro-tert-butoxide)} 以 乙醚 、 氘代苯 为溶剂， 生成 Mo(N-2,6-Me2C6H3)(CHCMe2Ph)[3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'-diolate]
  参考文献：
  名称：

  双烷氧基钼烯烃复分解催化剂的二苯基氨基前体。

  摘要：

  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]

  DOI：

  10.1021/om060430j
• 作为产物：
  描述：

  hexafluoro-tert-butanolate 、 Mo(N-2,6-Me₂-C₆H₃)(CHCMe₂Ph)(OTf)₂(DME) 以 乙二醇二甲醚 为溶剂， 以30%的产率得到{(2-methyl-2-phenyl-propylidene)((2,6-dimethylphenyl)imido)molybdenum(VI)bis(hexafluoro-tert-butoxide)}
  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
• 作为试剂：
  描述：

  2-氨基苯乙醇 在 草酰氯 、 {(2-methyl-2-phenyl-propylidene)((2,6-dimethylphenyl)imido)molybdenum(VI)bis(hexafluoro-tert-butoxide)} 、 三氟甲磺酸 、 sodium carbonate 、 氟化氢吡啶 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 11.92h， 生成 1-(N-trifluoroacetyl)-1,2,5,6-tetrahydro-5-(benzoxy)-1-benzazocine
  参考文献：
  名称：

  用于合成稠合氮杂环的闭环烯烃复分解

  摘要：

  已经开发出有效合成包含五元和八元环的各种组合的稠合氮杂环的新技术。该方法的特征在于由α，ω-二烯的钼亚烷基络合物6催化的闭环复分解（RCM），该α，ω-二烯在连接两个烯烃官能团的链中具有氮原子。

  DOI：

  10.1016/0040-4020(96)00249-9

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
• Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum
  作者：Smaranda C. Marinescu、Victor W. L. Ng、Alejandro G. Lichtscheidl、Richard R. Schrock、Peter Müller、Michael K. Takase

  DOI：10.1021/om300585s

  日期：2012.9.10

  2-CNPyr = 2-cyanopyrrolide), Mo(NAd)(CHCMe2Ph)(MesPyr)(OTPP) (2a; OTPP = 2,3,5,6-tetraphenylphenoxide), Mo(NAd)(CHCMe2Ph)(MesPyr)(OBr2Bitet) (2b; OBr2Bitet = (R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate), Mo(NAd)(CHCMe2Ph)(OHIPT)(2-Mespyr) (2c; HIPT = 2,6-(2,4,6-iPr3C6H2)2C6H3), Mo(NAd)(CHCMe2Ph)(OTf)(OHIPT) (3), Mo(NAd)(CHCMe2Ph)(OTf)(OHIPT)(PMe3)

  在本文中，我们描述了几种新型的钼金属立体异构金属亚胺基亚烷基络合物，Mo（NR）（CHR'）（X）（Y）的合成，其中许多必须通过选择性的亚氨基亲核取代反应来制备亚烷基络合物。报告的化合物包括Mo（NAd）（CHCMe 2 Ph）（MesPyr）2（1a ; MesPyr = 2-甲巯基吡咯化物，Ad = 1-金刚烷基），Mo（NAd）（CHCMe 2 Ph）（2-CNPyr）2（1b ; 2-CNPyr = 2-氰基吡咯化物），Mo（NAd）（CHCMe 2 Ph）（MesPyr）（OTPP）（2a ; OTPP = 2,3,5,6-四苯酚），Mo（NAd）（CHCMe 2 Ph） （MesPyr）（OBr 2 Bitet）（2b ; OBr2位=（R）-3,3'-二溴-2'-（叔丁基二甲基甲硅烷氧基）-5,5 '，6,6'，7,7'，8,8'-八氢-1,1'-联萘-2-酸），Mo（NAd）（CHCMe
• Synthesis of Alternating <i>trans</i>-AB Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Alkylidenes
  作者：Hyangsoo Jeong、Jeremy M. John、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1021/jacs.5b00221

  日期：2015.2.18

  metathesis polymerization (ROMP) with Mo(NR)(CHCMe2Ph)[OCMe(CF3)2]2 initiators (R = 2,6-Me2C6H3 (1) or 2,6-i-Pr2C6H3 (2)). The A:B monomer pairs copolymerized by 1 are cyclooctene (A):2,3-dicarbomethoxy-7-isopropylidenenorbornadiene (B), cycloheptene (A'):dimethylspiro[bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate-7,1'-cyclopropane] (B'), A:B', and A':B; A':B' and A:B' are also copolymerized by 2. The

  通过使用 Mo(NR)(CHCMe2Ph)[OCMe(CF3)2]2 引发剂（R = 2,6-Me2C6H3 (1) 或 2,6-i）的开环复分解聚合 (ROMP) 制备了四种交替 AB 共聚物-Pr2C6H3 (2))。1共聚的A:B单体对分别为环辛烯(A):2,3-二碳甲氧基-7-异亚丙基降冰片二烯(B)、环庚烯(A'):二甲基螺[双环[2.2.1]庚-2,5-二烯- 2,3-二羧酸酯-7,1'-环丙烷] (B')、A:B'和A':B；A':B' 和 A:B' 也由 2 共聚。>90% 的聚 (A-alt-B) 共聚物与具有反式构型的杂二联体 (AB) 形成。有证据表明，当 A（A 或 A'）与由 B 制成的亚烷基的顺式反应（syn-MB = syn-MB 或 syn-MB'）生成抗 MA 时，会形成一个反式杂 C=C 键, 而另一个反式 C=C 键是在 B 与 anti-MA 反应生成
• Synthesis of Oligo(1,6-heptadiynes) with a Single Structure and Terminal Methylene Groups Using Molybdenum-Based Wittig and Metathesis Chemistry. 1. 2,6-Dimethylphenylimido Systems
  作者：Corina Scriban、Richard R. Schrock、Peter Müller

  DOI：10.1021/om8007585

  日期：2008.12.8

  ORF6 = OCMe(CF3)2) gives [Mo][b][Mo]. An “Mo-Wittig” reaction between [Mo][b][Mo] and 2 equiv of the aldehyde, [CH2][b][O], then gives the “trimer”, [CH2][b3][CH2]. Treatment of [CH2][b3][CH2] with 2 equiv of [Mo][CHCMe2Ph] gives [Mo][b3][Mo], which upon treatment with 2 equiv of [CH2][b][O] gives the “pentamer”, [CH2][b5][CH2], which contains 11 double bonds in conjugation in a molecule in which the

  在本文中，我们演示了一种合成二异丙基二炔丙基丙二酸丙二酯[CH 2 ] [b x ] [CH 2 ]（x = 2，3，4，5）的低聚物的方法，其中“ b”重复单元与五个重复单元相同。二异丙基二炔丙基丙二酸酯的尾到尾环聚合反应中形成的二元环和亚甲基封端。例如，“单体”，[CH 2 ] [b] [CH 2 ]和2当量的Mo（NAr'）（CHCMe 2 Ph）（OR F6）2（[Mo] [CHCMe 2 Ph]其中Ar'= 2,6-Me 2 C 6 H 3和F6＝ OCMe（CF 3）2）给出[Mo] [b] [Mo]。[Mo] [b] [Mo]与2当量的醛[CH 2 ] [b] [O]之间进行“ Mo-Wittig”反应，然后得到“三聚体” [CH 2 ] [b 3 ] [CH 2 ]。用2当量的[Mo] [CHCMe 2 Ph]处理[CH 2 ] [b 3 ] [CH 2 ]得到[Mo] [b
• In situ NMR investigations into the ADMET-reaction of 1,4-diheptyloxy-2,5-divinylbenzene via a Schrock-type molybdenum alkylidene complex
  作者：Ralf M. Peetz、Volker Sinnwell、Emma Thorn-Csányi

  DOI：10.1016/j.molcata.2006.01.069

  日期：2006.7

  The acyclic diene metathesis (ADMET) polycondensation of 1,4-diheptyloxy-2,5-divinylbenzene (DHepODVB) with the Schrock-type alkylidene complex Mo(NArMe2)(CHCMe2Ph)[OCMe(CF3)(2)](2) was investigated by means of in situ H-1/C-13 NMR spectroscopy. Efforts were made to a gain insight into the reaction mechanism and explain the relatively high reaction temperatures (> 60 degrees C instead of room temperature in the case of the diheptylsubstituted analog) necessary to achieve useful reaction rates. Different reaction charges were investigated in dependence on reaction time and ratio catalyst/monomer. At least four novel alkylidene species were detected of which three species could be assigned to structures (two of which are binuclear, presumably due to the nearly stoichiometric ratios catalyst/monomer). These three structures show a Mo-coordination from the oxygen of a heptyloxy side chain from the substrate resulting in stabilized intermediates. These intermediates act as low energy "traps" that make the higher reaction temperatures necessary. The stabilization also seems to effect decomposition of active species, substantially slowing it down. Even after 24 days, alkylidene signals could be detected without noticeable reduction in relative amount. (c) 2006 Elsevier B.V. All rights reserved.