Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(OTf)2(DME) | 645391-49-7

• 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-i-Pr2C6H3)(CHCMe2Ph)(OTf)2(DME)
• CAS: 645391-49-7
• 化学式: C₂₈H₃₉F₆MoNO₈S₂
• 分子量: 791.682
• InChiKey: NLTJIWBSURFRCN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  46
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  162
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  2,6-dichlorophenol lithium 、 Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(OTf)2(DME) 在 pyridine 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以58%的产率得到Mo(CHCMe2PH)(N-2,6-diisopropylphenyl)(O-2,6-dichlorophenoxide)2(pyridine)
  参考文献：
  名称：

  Monoadducts of imido alkylidene complexes, syn and anti rotamers, and alkylidene ligand rotation

  摘要：

  Complexes of the type M(CH-t-Bu)(NAr)(OR)2 (M = Mo, W; Ar = 2,6-C6H3-i-Pr2; OR = OCMe(CF3)2, OCMe2(CF3)) form five-coordinate adducts upon addition of PMe3 or quinuclidine. PMe3 attacks the C/N/O face of the pseudotetrahedral complexes to give chiral TBP species in which the phosphine is bound in an axial position and the imido and alkylidene ligands lie in the equatorial plane. Two isomers containing syn and anti rotamers of the alkylidene ligand are observed. The syn rotamer forms first; the anti rotamer is the final product. PMe3 binds weakly when OR = O-t-Bu and is lost readily in vacuo. Quinuclidine adds to either the C/O/O face or N/O/O face to give an achiral syn isomer and to the C/N/O face to give an anti chiral TBP species analogous to that formed for the PMe3 adduct. An equilibrium mixture of syn and anti forms is observed with time. An X-ray structure of syn-Mo(CH-t-Bu)(NAr)[OCMe(CF3)2]2(PMe3) shows that the t-Bu group points toward the imido ligand and the phenyl ring of the imido ligand lies approximately in the equatorial plane in a relatively crowded coordination environment (a = 10.979 (4) angstrom, b = 17.945 (7) angstrom, c = 18.375 (8) angstrom, beta = 106.34 (3)degrees, Z = 4, V = 3474 (4) angstrom 3, rho = 1.490 g/cm3, R = 0.037, R(w) = 0.045). Pyridine adducts of Mo complexes containing the 2,6-dichlorophenoxide ligand also have been characterized. Three isomers of five-coordinate molybdenum or tungsten complexes containing a cis- or trans-2-butenylidene ligand and quinuclidine are found at equilibrium, syn and anti rotamers of the chiral core previously described and a syn rotamer with an achiral core. An X-ray structure of anti-W(trans-CHCH = CHMe)(NAr)[OCMe(CF3)2]2(quin) showed the expected trigonal-bipyramidal core with alkylidene and imido ligands occupying equatorial sites and OCMe(CF3)2 ligands occupying one axial and one equatorial site (a = 12.972 (9) angstrom, b = 18.049 (7) angstrom, c = 15.038 (9) angstrom, beta = 92.07 (3)degrees, Z = 4, V = 3518 (6) angstrom 3, rho = 1.673 g/cm3, R1 = 0.038, R(w) = 0.040). The only significant difference between the structure of this anti adduct and the syn adduct described above is that the anti adduct is markedly less crowded in the equatorial plane. Syn and anti rotamers in five-coordinate adducts have been shown to interconvert after losing the base in several cases. The barrier to rotation of the alkylidene ligand has been measured in several four-coordinate species and shown to lie in the range DELTA-G-double-ended-dagger 298 = 15-18 kcal mol-1. These findings are discussed in relation to the proposed mechanism of olefin metathesis by pseudotetrahedral complexes of the type M(CHR')(NAr)(OR)2.

  DOI：

  10.1021/om00052a033
• 作为产物：
  描述：

  N-trimethylsilyl-2,6-diisopropylaniline 在 2,6-lutidine 、 chlorotrimethylsilane 作用下， 以 乙二醇二甲醚 、 乙醚 为溶剂， 生成 Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(OTf)2(DME)
  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, X-ray structure and reactivity of μ-(CF3COO)2-[Mo(N-2,6-i-Pr2-C6H3)(CHCMe2Ph)(OOCCF3)(Et2O)]2, the first Bis(trifluoroacetate) derivative of a Schrock catalyst
  作者：Michael R. Buchmeiser、Dongren Wang、Sergej Naumov、Klaus Wurst

  DOI：10.1016/j.jorganchem.2006.08.087

  日期：2006.12

  Reaction of Mo(N-2,6-i-Pr2-C6H3)(CHCMe2C6H5)(OSO2CF3)(DME) (DME = 1,2-dimethoxyethane) with 2 equiv. of CF3COOK yields μ-(CF3COO)2-[Mo(N-2,6-i-Pr2-C6H3)(CHCMe2Ph)(OOCCF3)(Et2O)]2 (1). Compound 1 crystallizes in the orthorhombic space group Pna21 with a = 17.2485(3), b = 17.0336(3), c = 25.4031(5) Å, α = β = γ = 90°, V = 7463.5(2) Å3, Z = 4. In contrast to alkoxide based Schrock type initiators, 1 is

  Mo（N- 2,6 - i - Pr 2 -C 6 H 3）（CHCMe 2 C 6 H 5）（OSO 2 CF 3）（DME）（DME = 1,2-二甲氧基乙烷）的反应 CF 3 COOK的产率为μ-（CF 3 COO）2- [Mo（N-2,6- i -Pr 2 -C 6 H 3）（CHCMe 2 Ph）（OOCCF 3）（Et 2 O）] 2（1）。化合物1在正交空间群Pna2 1中结晶与一个 = 17.2485（3），b  = 17.0336（3），C ^  = 25.4031（5）中，α=β=γ= 90°，V  = 7463.5（2）埃3，ž  = 4相比于基于醇盐Schrock型引发剂1在许多复分解反应中几乎没有活性，包括闭环复分解（RCM）和均复分解反应，1,6-庚二炔的环聚合，甚至降冰片2-烯的开环复分解聚合（ROMP） 。但是，添加奎宁环素会原位形成1a（Mo（N-2,6-
• Molybdenum Imido Alkylidene Complexes that Contain a β-Diketiminate Ligand
  作者：Zachary J. Tonzetich、Annie J. Jiang、Richard R. Schrock、Peter Müller

  DOI：10.1021/om7003207

  日期：2007.7.1

  The molybdenum β-diketiminate complexes Mo(NR)(CHCMe2R‘)(Ar-nacnac)(OTf) (R = 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 1-adamantyl, 2,6-dichlorophenyl, or 2-tert-butylphenyl; Ar = 2,6-dichlorophenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, or 2,6-difluorophenyl; R‘ = Me or Ph; Ar-nacnac = [ArNC(Me)]2CH; OTf = trifluoromethanesulfonate) have been prepared from Mo(NR)(CHCMe2R‘)(OTf)2(DME) by metathesis

  β-二酮钼配合物Mo（NR）（CHCMe 2 R'）（Ar-nacnac）（OTf）（R = 2,6-二异丙基苯基，2,6-二甲基苯基，1-金刚烷基，2,6-二氯苯基或2-叔丁基苯基； Ar = 2,6-二氯苯基，2,6-二甲基苯基，3,5-二甲基苯基或2,6-二氟苯基； R'= Me或Ph; Ar-nacnac = [ArNC（Me）]通过与相应的Li Ar-nacnac}盐复分解，由Mo（NR）（CHCMe 2 R'）（OTf）2（DME）制备2 CH； OTf =三氟甲磺酸盐。Mo（NR）（CHCMe 2 R'）（Ar-nacnac）（OTf）与NaBAr f4（Ar f = 3,5-（CF 3）2 C 6 H 3）存在或不存在THF的情况下，根据Ar的性质，可提供阳离子物种Mo（NR）（CHCMe 2 R'）（Ar-nacnac）（THF）n } BAr f4 }（n = 0或1）
• Syntheses of Molybdenum(VI) Imido Alkylidene Complexes That Contain a Bidentate Dithiolate Ligand
  作者：Hosein Tafazolian、Charlene Tsay、Richard R. Schrock、Peter Müller

  DOI：10.1021/acs.organomet.8b00614

  日期：2018.11.12

  respectively. Complexes that contain a 3,3′,5,5′-tetrasubstituted dithiabiphenolate were prepared in a reaction between Mo(NAr)(CHCMe2Ph)(Me2pyr)2 (Me2pyr = 2,5-dimethylpyrrolide) and the 3,3′,5,5′-tetrasubstituted dithiabiphenols, (3,3′,5,5′-tetrachlorodithiabiphenol (H2Cl4S2), 3,3′,5,5′-tetrabromodithiabiphenol (H2Br4S2), and 3,3′,5,5′-tetra-t-Bu-dithiabiphenol (H2Bu4S2)). The isolated complexes include

  Zn（DCTC）（DCTC = 3,6-dichlorodithiacatecholate）与Mo（NAd）（CHCMe 2 Ph）Cl 2（PPh 2 Me）（Ad = 1-金刚烷基）反应生成Mo（NAd）（CHCMe 2 Ph）（ DCTC）（PPh 2 Me）。Zn（DCTC）与Mo（NAd）（CH- t- Bu）（OTf）2（dme）或Mo（NAr）（CHCMe 2 Ph）（OTf）2（dme）之间的反应（Ar = 2,6- i -Pr 2 C 6 H 3； OTf =三氟甲磺酸盐； dme = 1,2-二甲氧基乙烷）产生[Mo（NAd）（CH- t- Bu）（DCTC）] 2和[Mo（NAr）（CHCMe 2 Ph） （DCTC）] 2， 分别。在Mo（NAr）（CHCMe 2 Ph）（Me 2 pyr）2（Me 2 pyr = 2,5-二甲基吡咯化物）与M（NAr）（CHCMe
• Simple Molybdenum(IV) Olefin Complexes of the Type Mo(NR)(X)(Y)(olefin)
  作者：Smaranda C. Marinescu、Annie J. King、Richard R. Schrock、Rojendra Singh、Peter Müller、Michael K. Takase

  DOI：10.1021/om101003v

  日期：2010.12.27

  Mo(NAr)(C4H8)(OSiPh3)2 (10), is generated. X-ray structural studies were carried out on 2c, 5a, 6, 8, 9a, and 10. All evidence suggests that alkene exchange at the Mo(IV) center is facile, followed by cis,trans isomerization and isomerization via double bond migration. In addition, trace amounts of alkylidene complexes are formed that result in slow metathesis reactions of free olefins to give (e.g.) a distribution

  Mo（NAr）（CHCMe 2 Ph）（Me 2 Pyr）（OAr）（1a ; Ar = 2,6-二异丙基苯基），Mo（NAr）（CHCMe 3）（Me 2 Pyr）[OCMe（ CF 3）2 ]（1b）和Mo（NAr）（CHCMe 2 Ph）（Me 2 Pyr）（OSiPh 3）（1c）在一个乙烯气氛中反应12 h，得到乙烯络合物Mo（NAr）（CH 2 CH 2）（Me 2 Pyr）（OAr）（2a），Mo（NAr）（CH 2 CH 2）（Me 2 Pyr）[OCMe（CF 3）2 ]（2b），和Mo（NAr）（CH 2 CH 2）（Me 2 Pyr）（OSiPh 3）（2c）。将1当量的三苯基硅烷醇加到2c的溶液中，容易得到Mo（NAr）（CH 2 CH 2）（OSiPh 3）2（3）。Mo（NAr）（CHCMe 2 Ph）（OTf）2（dme）与乙烯（60 psi）在甲苯中于80°C缓慢反应，生成Mo（NAr）（CH
• N-Heterocyclic Carbene Complexes Of Metal Imido Alkylidenes And Metal OXO Alkylidenes, And The Use Of Same
  申请人：UNIVERSITÄT STUTTGART

  公开号：US20170050994A1

  公开（公告）日：2017-02-23

  The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2′, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2′ stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1′ in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.

  该发明涉及一种N-杂环卡宾复合物，其一般公式为I至IV（I）（II）（III）（IV），其中A1代表NR2或PR2，A2代表CR2R2′，NR2，PR2，0或S，A3代表N或P，C代表卡宾碳原子，环B为未取代或单取代或多取代的5至7元环，取代基R2和R2′代表线性或支链的C1-Cw-烷基基团，如果N和N分别代表NR2或PR2，则它们可以相同也可以不同，公式I、II、III或IV中的M代表Cr、Mo或W，公式I至IV中的X1或X2是相同或不同的，代表C1-C1s羧酸盐和C1-C1s-烷氧基等，Y为氧或硫等，Z为线性或支链的C1-Cw-烷氧基基团等，公式I至IV中的R1和R1′为脂肪族或芳香族基团等。这些化合物特别适用作为烯烃重排反应的催化剂，并相比已知的Schrock卡宾复合物，具有明显增强的对官能团的耐受性，特别是对醛、二级胺、腈、羧酸和醇等的耐受性增强。