{(neophylidene)(2,6-diisopropylphenylimido)(2-tert-butylphenoxide)2 molybdenum} | 127061-12-5

• 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: {(neophylidene)(2,6-diisopropylphenylimido)(2-tert-butylphenoxide)2 molybdenum}
• 英文别名: 2-Tert-butylphenolate;[2,6-di(propan-2-yl)phenyl]imino-(2-methyl-2-phenylpropylidene)molybdenum(2+)；2-tert-butylphenolate;[2,6-di(propan-2-yl)phenyl]imino-(2-methyl-2-phenylpropylidene)molybdenum(2+)
• CAS: 127061-12-5；126949-64-2；134452-75-8
• 化学式: C₄₂H₅₅MoNO₂
• 分子量: 701.844
• InChiKey: KQMGJESXPXPSNI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  10.73
• 重原子数：
  46
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  58.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  {(neophylidene)(2,6-diisopropylphenylimido)(2-tert-butylphenoxide)2 molybdenum} 、 乙烯基二甲基乙氧基硅烷 以 乙醚 为溶剂， 以60%的产率得到Mo(CHSi(OEt)Me2)(N-2,6-diisopropylphenyl)(2-tert-butylphenoxide)2
  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 {(neophylidene)(2,6-diisopropylphenylimido)(2-tert-butylphenoxide)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 molybdenum imido alkylidene complexes and some reactions involving acyclic olefins
  作者：Richard R. Schrock、John S. Murdzek、Gui C. Bazan、Jennifer Robbins、Marcello DiMare、Marie O'Regan

  DOI：10.1021/ja00166a023

  日期：1990.5

  of the type Mo(C-t-Bu)(NHAr)(OR)sub 2} (OR = OCMe(CFsub 3})sub 2} or OAr) have been prepared from 1, but they cannot be transformed into Mo(CH-t-Bu)(NAr)(OR)sub 2} complexes. A precursor to imido alkylidene complexes that is related to 2 has been prepared by the sequence MoOsub 2} yields} MoOsub 2}Clsub 2} yields} Mo(NAr)sub 2}Clsub 2} yields} Mo(NAr)sub 2}(CHsub 2}Rprime})sub 2} yields}

  Mo(Ct-Bu)(dme)Clsub 3} (dme = 1,2-二甲氧基乙烷) 和 Mesub 3}SiNHAr (Ar = 2,6-二异丙基苯基) 反应生成 Mo(Ct-Bu)( NHAr)Clsub 2}(dme) (1)，在用催化量的 NEtsub 3} 处理后转化为 Mo(CH-t-Bu)(NAr)Clsub 2}(dme) ( 2）。Mo(CH-t-Bu)(NAr)(OR)sub 2} (OR = OCMe(CFsub 3})sub 2}, OCMesub 2}(CFsub 3}) 、Ot-Bu 或 OAr) 已由 2. Mo(Ct-Bu)(NHAr)(OR)sub 2} (OR = OCMe(CFsub 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
• Monoadducts of imido alkylidene complexes, syn and anti rotamers, and alkylidene ligand rotation
  作者：Richard R. Schrock、William E. Crowe、Guillermo C. Bazan、Marcello DiMare、Marie B. O'Regan、Mark H. Schofield

  DOI：10.1021/om00052a033

  日期：1991.6

  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.