W(CH-t-Bu)(N-2,6-diisopropylphenyl)(hexafluoro-tert-butoxide)2 | 101249-40-5

• 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: W(CH-t-Bu)(N-2,6-diisopropylphenyl)(hexafluoro-tert-butoxide)2
• 英文别名: W(=CHtBu)(=N-2,6-iPr2C6H3)[OCMe(CF3)2]2
• CAS: 101249-40-5
• 化学式: C₂₅H₃₃F₁₂NO₂W
• 分子量: 791.373
• InChiKey: DJPNRTQAGZAQEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.85
• 重原子数：
  41.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  32.56
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  W(CH-t-Bu)(N-2,6-diisopropylphenyl)(hexafluoro-tert-butoxide)2 在 acetone 作用下， 以 not given 为溶剂， 以>99的产率得到bis(1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl) (2,6-diisopropylphenyl)imidtungstate
  参考文献：
  名称：

  多重金属-碳键。43. 特性良好的高活性无路易斯酸烯烃复分解催化剂

  摘要：

  制备和活性 d'un complexe de W de type W(CH-t-Bu)(NR)(OR') 2 , OR'=OC(Me)(CF 3 ) 2

  DOI：

  10.1021/ja00270a056
• 作为产物：
  描述：

  W(=CHtBu)(=N-2,6-iPr2C6H3)Cl2(dme) 、 1,1,1,3,3,3-六氟-2-甲基-2-丙醇 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 W(CH-t-Bu)(N-2,6-diisopropylphenyl)(hexafluoro-tert-butoxide)2
  参考文献：
  名称：

  PROCESS FOR PRODUCING ORGANIC TRANSITION METAL COMPLEX COMPOUND

  摘要：

  公开号：

  EP1950216B1
• 作为试剂：
  描述：

  顺-4-壬烯 在 W(CH-t-Bu)(N-2,6-diisopropylphenyl)(hexafluoro-tert-butoxide)2 作用下， 以 甲苯 为溶剂， 反应 0.05h， 生成 4-octene 、 5-癸烯
  参考文献：
  名称：

  d 0二氧化硅负载的（SiO）W（NAr）（CHtBu）（OR）催化剂中OR配体σ给予的量级及其对烯烃复分解活性的影响

  摘要：

  通过接枝制备的通式[（SiO）W（NAr）（CHtBu）（OR）]（OR = OtBu F9，OtBu F6，OtBu F3，OtBu和OSi（OtBu）3）的轮廓分明的二氧化硅负载W催化剂在700°C下脱羟基的二氧化硅上的双醇盐配合物[W（NAr）（CHtBu）（OR）2（SiO 2（700））与其Mo同系物相比显示出乎意料的高活性。在该系列中，顺式-4-壬烯的自我复分解活性随OR配体的增加而增加，如下所示：OtBu

  DOI：

  10.1039/c4sc00230j

文献信息

• Further studies of imido alkylidene complexes of tungsten, well-characterized olefin metathesis catalysts with controllable activity
  作者：Richard R. Schrock、R. T. DePue、J. Feldman、K. B. Yap、D. C. Yang、W. M. Davis、L. Park、M. DiMare、M. Schofield

  DOI：10.1021/om00158a025

  日期：1990.8
• Double Phosphaalkyne Insertion to a Tungsten Alkylidene:  Formation of a Diphosphametallabicyclobutane
  作者：Gregory M. Jamison、David R. Wheeler、Douglas A. Loy、Joseph W. Ziller

  DOI：10.1021/om050150o

  日期：2005.5.1

  A unique diphosphametallabicyclobutane complex results from the reaction of the Schrock tungsten neopentylidene with excess P equivalent to C-t-Bu, in contrast to phosphaalkyne reaction products with similar molybdenum alkylidenes. A mechanistic rationalization for the complex, which has been structurally characterized by NMR spectroscopy and single-crystal X-ray analysis, is postulated in terms of a ring-opening metathesis-like mechanism.
• 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.