{(2-methyl-2-phenyl-propylidene)((2,6-diisopropylphenyl)imido)molybdenum(VI)bis(trifluoro-tert-butoxide)} | 149883-25-0

• 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: {(2-methyl-2-phenyl-propylidene)((2,6-diisopropylphenyl)imido)molybdenum(VI)bis(trifluoro-tert-butoxide)}
• 英文别名: (2,6-diisopropylphenylimido)bis(1,1-dimethyl-2,2,2-trifluoroethanolato)Mo(PhMe2CCH)；PhMe2CCH=Mo(2,6-diisopropylphenylimido)(1,1-dimethyl-2,2,2-trifluoroethanolato)2；[Mo(N(2,6-(i)Pr2C6H3))(CHCMe2Ph)(trifluoro-tert-butoxide)2]；PhMe2C-CH=Mo(N(2,6-i-Pr2C6H3))(OCMe2CF3)2；[PhMe2CCH=Mo(2,6-(i-Pr)2C6H3)(OCMe2CF3)2]；PhMe2CCH=Mo(N-2,6-iPr2C6H3)(OCMe2Ph)2
• CAS: 149883-25-0；149883-24-9；135505-85-0
• 化学式: C₃₀H₄₁F₆MoNO₂
• 分子量: 657.591
• InChiKey: PUJPUHOBGKQGPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.23
• 重原子数：
  40.0
• 可旋转键数：
  9.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 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-diisopropylphenyl)imido)molybdenum(VI)bis(trifluoro-tert-butoxide)} 、 乙烯基(三苯基)锗烷 以 苯 为溶剂， 以65%的产率得到
  参考文献：
  名称：

  带有直接锗碳碳键的钼R 3 Ge–CHMo（NAr）（OR'）2（R = Me，Ph）的第一批含锗亚烷基配合物的合成和晶体结构

  摘要：

  通过以下方法制备了新型的含钼的R 3 Ge–CHMo（NAr）（OCMe 2 CF 3）2（Ar = 2,6- i -Pr 2 C 6 H 3； R = Me，Ph）的亚烷基络合物。有机锗乙烯基试剂R 3 GeCHCH 2与已知的亚烷基化合物烷基–CHMo（NAr）（OCMe 2 CF 3）2（烷基= Bu t，PhMe 2 C）的反应。分离出标题化合物，为结晶固体，并通过元素分析，1 H NMR，13进行表征C NMR光谱和X射线衍射研究。化合物中Mo原子的几何形状可描述为扭曲的四面体。

  DOI：

  10.1016/j.jorganchem.2005.02.051
• 作为产物：
  描述：

  Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(OTf)2(DME) 、 2-(trifluoromethyl)-2-propoxide ion 以 乙二醇二甲醚 为溶剂， 以53%的产率得到{(2-methyl-2-phenyl-propylidene)((2,6-diisopropylphenyl)imido)molybdenum(VI)bis(trifluoro-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：

  rac-(R)-9-methoxy-10b-((S)-2-methoxypent-4-en-1-yl)-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-1(10bH)-one 在 {(2-methyl-2-phenyl-propylidene)((2,6-diisopropylphenyl)imido)molybdenum(VI)bis(trifluoro-tert-butoxide)} 作用下， 以 苯 为溶剂， 反应 15.0h， 以84%的产率得到衡州乌药定
  参考文献：
  名称：

  喹啉和异喹啉丙炔醇的质子溶剂介导的环异构化：(±)-3-去甲氧基异戊四烯酮和 (±)-Cocculidine 的合成

  摘要：

  将“苯”放入吲哚嗪酮中：苯并[ g ] 吲哚嗪酮和苯并[ e ] 吲哚嗪酮的环异构化方法为这些独特的氮杂环提供了第一条通用路线（参见示例）。通过将这种方法应用于刺桐生物碱 3-脱甲氧基赤霉啶酮和球虫碱的全合成，证明了苯并吲哚嗪酮产品的实用性。

  DOI：

  10.1002/anie.201304687

文献信息

• Synthesis and some properties of 14 group element-containing alkylidene complexes of molybdenum and tungsten
  作者：Leonid N. Bochkarev、Yulia E. Begantsova、Vladislav I. Shcherbakov、Natalia E. Stolyarova、Irina K. Grigorieva、Irina P. Malysheva、Galina V. Basova、Andrey L. Bochkarev、Yulia P. Barinova、Georgii K. Fukin、Evgenii V. Baranov、Yurii A. Kurskii、Gleb A. Abakumov

  DOI：10.1016/j.jorganchem.2005.07.035

  日期：2005.12

  and tungsten (ArN)2M(CH2EMe3)2 (Ar=2,6-Pr2iC6H3; M = Mo. W; E = Si, Ge, Sn) with triflic acid were shown to yield a complex mixture of products among which carbene complexes have not been observed. The formation of carbene complexes of tungsten in low yields was observed by 1H NMR spectroscopy in the reactions of (ArN)2W(CH2EMe3)2 (E = Si, Ge, Sn) with hydrogen chloride in THF-d8. Catalytic properties

  亚烷基络合物钼的Ph 3硅- CHMo（NAR）（OCME 2 CF 3）2（1）（Ar为2,6- Pr2iC6H3）已经准备通过pH的反应3 SiCHCH 2与已知的亚烷基化合物烷基- CHMo（ NAr）（OCME 2 CF 3）2（烷基＝ Bu t，PhMe 2 C）。根据X射线衍射研究，（1）中Mo原子的几何形状可描述为扭曲的四面体。钼和钨（ArN）2 M（CH 2 EMe3）2（Ar = 2,6-Pr2iC6H3 ; M = Mo. W; E = Si，Ge，Sn）与三氟甲磺酸显示出产物的复杂混合物，其中未观察到卡宾络合物。通过1 H NMR光谱在（ArN）2 W（CH 2 EMe 3）2（E = Si，Ge，Sn）与氯化氢在THF- d 8中的反应中观察到低产率的钨卡宾配合物的形成。R 3 E – CHMo（NAr）（OCME 2 CF 3）2的含杂元素的亚烷基络合物的催化性能（E
• Synthesis and reactivity of molybdenum imido alkylidene bis-pyrazolide complexes
  作者：David Gajan、Nuria Rendón、Keith M. Wampler、Jean-Marie Basset、Christophe Copéret、Anne Lesage、Lyndon Emsley、Richard R. Schrock

  DOI：10.1039/c0dt00315h

  日期：——

  Reaction of Li(3,5-R2-pyrazolide) (R = tBu or Ph, dXpz) with Mo(NAr)(CHCMe2Ph)(OTf)2(DME) yields Mo(NAr)(CHCMe2Ph)(dXpz)2 in good yield. These complexes react with alcohols or the surface silanols of silica, to yield bis-alkoxy and surface mono-siloxy alkene metathesis catalysts, respectively.

  Li(3,5-R2-pyrazolide) (R = tBu 或 Ph, dXpz) 与 Mo(NAr)(CHCMe2Ph)(OTf)2(DME) 反应生成 Mo(NAr)(CHCMe2Ph)(dXpz)2，收率很高。这些配合物与醇类或二氧化硅的表面硅烷醇反应，分别生成双烷氧基和表面单硅氧烷复分解催化剂。
• Pairwise ligand exchange reactions in tetrahedral and pseudo-tetrahedral transition metal complexesElectronic supplementary information (ESI) available: Experimental procedures for synthesis of new compounds and for NMR-scale ligand exchange reactions as well as 1H NMR spectroscopic data characterising products of these reactions. See http://www.rsc.org/suppdata/dt/b3/b308062e/
  作者：Vernon C. Gibson、Andrew J. Graham、Matthew Jolly、Jonathan P. Mitchell

  DOI：10.1039/b308062e

  日期：——

  Ligand exchange reactions between various transition-metal complexes of the form [Mo(Q)2X2], [M(Q)CpX2] and [Mo(Q)2CpX], where Q and X are di-anionic and mono-anionic ligands, respectively, and M is Nb or Ta, have been studied. The formal electron count at the metal, and also the steric and electronic properties of the supporting ligands, are found to influence exchange rates, while ligand steric and electronic properties affect equilibrium constants.

  研究了[Mo(Q)2X2]、[M(Q)CpX2]和[Mo(Q)2CpX]形式的各种过渡金属配合物之间的配体交换反应，其中 Q 和 X 分别为二阴离子和单阴离子配体，M 为 Nb 或 Ta。研究发现，金属的形式电子数以及支持配体的立体和电子特性会影响交换率，而配体的立体和电子特性则会影响平衡常数。
• Carbene complexes of molybdenum and tungsten Et3E-CH=M(NAr)(OR)2 (M = Mo, W; E = Si, Ge) and π-complex of molybdenum (RO)2(ArN)Mo(CH2=CH-GeEt3). Synthesis and catalytic properties
  作者：Yu. P. Barinova、A. L. Bochkarev、Yu. E. Begantsova、L. N. Bochkarev、Yu. A. Kurskii、G. K. Fukin、A. V. Cherkasov、G. A. Abakumov

  DOI：10.1134/s1070363210100129

  日期：2010.10

  heteroelement-containing alkylidene imide complexes with molybdenum and tungsten Et3SiCH=Mo(NAr)(OR)2 (I), Et3 ECH=W(NAr)(OR)2 (E = Si (II), Ge (III); Ar = 2,6-i-Pr2C6H3; R=CMe2 CF3) and π-complex (RO)2(ArN)Mo(CH2=CH-GeEt3) (IV) were synthesized by the reaction of Alkyl-CH=M(NAr) (OR)2 (M=Mo, W; Alkyl = t-Bu, PhMe2C) with organosilicon and organogermanium vinyl reagents Et3ECH=CH2 (E = Si, Ge). The

  含杂元素的亚钼酰亚胺与钼和钨的络合物Et 3 SiCH = Mo（NAr）（OR）2（I），Et 3 ECH = W（NAr）（OR）2（E = Si（II），Ge（III）;合成Ar = 2,6- i -Pr 2 C 6 H 3 ; R = CMe 2 CF 3）和π络合物（RO）2（ArN）Mo（CH 2 = CH-GeEt 3）（IV）通过烷基-CH = M（NAr）（OR）2（M = Mo，W;烷基= t -Bu，PhMe 2C）用有机硅和有机锗乙烯基试剂Et 3 ECH = CH 2（E = Si，Ge）。化合物I–III的结构通过X射线衍射（XRD）确定。配合物I–IV是环烯烃复分解聚合的活性引发剂。
• Molybdenum tin-containing π-complexes (R3SnCH=CH2)Mo(N-2,6-Pr 2 i -C6H3)(OCMe2CF3)2· Synthesis and catalytic properties
  作者：Yu. P. Barinova、L. N. Bochkarev、Yu. A. Kurskii、G. A. Abakumov

  DOI：10.1134/s1070363212010033

  日期：2012.1

  The tin-containing molybdenum π-complexes (R3SnCH=CH2)Mo(N-2,6-Pri 2C6H3)(OCMe2CF3)2 (R = Me, Et, Ph) were synthesized by reaction of PhMe2CCH=Mo(N-2,6-Pri 2C6H3)(OCMe2CF3)2 with organotin vinyl reagents R3SnCH=CH2. The structure of compounds I–III was determined by NMR spectroscopy. Complexes I–III are active initiators of the norbornene metathesis polymerization.

  合成了含锡的钼π络合物（R 3 SnCH = CH 2）Mo（N-2,6-Pr i 2 C 6 H 3）（OCMe 2 CF 3）2（R = Me，Et，Ph）通过使PhMe 2 CCH = Mo（N-2,6-Pr i 2 C 6 H 3）（OCMe 2 CF 3）2与有机锡乙烯基试剂R 3 SnCH = CH 2反应。化合物I–III的结构通过NMR光谱测定。I–III配合物 是降冰片烯复分解聚合反应的活性引发剂。