Li(NC5H4(CPh2O)-2) | 149064-19-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Li(NC5H4(CPh2O)-2)
• CAS: 149064-19-7
• 化学式: C₁₈H₁₄LiNO
• 分子量: 267.256
• InChiKey: PEPWTVGSICOLJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.26
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  35.95
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  W(NPh)Cl₄(Et₂O) 、 Li(NC5H4(CPh2O)-2) 以 乙醚 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  Van Der Schaaf, Paul A.; Boersma, Jaap; Smeets, Wilbert J. J., Inorganic Chemistry, 1993, vol. 32, # 23, p. 5108 - 5113

  摘要：

  DOI：

文献信息

• Polymerization of Ethylene by the Electrophilic Mixed Cyclopentadienylpyridylalkoxide Complexes [CpM{NC₅H₄(CR₂O)-2}Cl₂] (M = Ti, Zr, R = Ph, Prⁱ)
  作者：Simon Doherty、R. John Errington、Adam P. Jarvis、Scott Collins、William Clegg、Mark R. J. Elsegood

  DOI：10.1021/om980222u

  日期：1998.8.1

  [CpMNC5H4(CR2O)-2}Cl2] (M = Ti; R = Pri (1a), Ph (1b); M = Zr, R = Pri (2a), Ph (2b)) have been prepared and characterized. Single-crystal X-ray analyses reveal that 1a and 2b adopt four-legged piano-stool structures in which the cyclopentadienyl ligand is asymmetrically bonded and the pyridylalkoxide is bidentate. Toluene solutions of [CpMNC5H4(CR2O)-2}Cl2] and methylaluminoxane catalyze the polymerization

  第4组混合配体化合物[CpM NC 5 H 4（CR 2 O）-2} Cl 2 ]（M = Ti； R = Pr i（1a），Ph（1b）； M = Zr，R = Pr i（2a），Ph（2b））已制备并表征。X射线单晶分析表明1a和2b采用四腿钢琴凳结构，其中环戊二烯基配体不对称键合，吡啶基醇盐为双齿。[CpM NC 5 H 4（CR 2 O）-2} Cl 2的甲苯溶液]和甲基铝氧烷催化乙烯的聚合反应，生成分子量分布窄的高分子量聚合物。钛和锆基催化剂的活性是可比的。
• A new type of tungsten(<scp>VI</scp>) phenylimido alkylidene complex and its triorganotungsten precursor with an O,N-chelating ligand; molecular structures of [W(CH₂SiMe₃)₃(NPh){OCPh₂(2-py)}] and [W{CHSiMe₃(CH₂SiMe₃)(NPh){OCPh₂(2-py)}](py = pyridine)
  作者：Paul A. van der Schaaf、Rob A. T. M. Abbenhuis、David M. Grove、Wilberth J. J. Smeets、Anthony L. Spek、Gerard van Koten

  DOI：10.1039/c39930000504

  日期：——

  A new type of tungsten(VI) alkylidene complex has been prepared with [OCPh2(2-py)], a potentially bidentate O,N-chelating monoanionic ligand, and the corresponding triorganotungsten phenylimido alkoxide precursor complexes have been isolated; the new tungsten(VI) alkylidene complex [W(CHSiMe3)(CH2SiMe3)(NPh)-OCPh2(2-py)}]3 reacts with norbornene (70 °C) to provide selectively the cis-polymer in a

  用[OCPh 2（2-py）]，一种潜在的双齿O，N-螯合单阴离子配体制备了一种新型的钨（VI）亚烷基配合物，并分离了相应的三有机钨苯基亚氨基醇盐前体配合物；新的钨（VI）亚烷基络合物[W（CHSiMe 3）（CH 2 SiMe 3）（NPh）-OCPh 2（2-py）}] 3与降冰片烯（70°C）反应，选择性地提供顺式聚合物在开环易位聚合反应中。
• Tungsten(VI) phenylimido alkylidene complexes containing a monoanionic O,N-chelating ligand and their isolated precursor complexes: x-ray structures of W(CH2SiMe3)3(:NPh)[OCPh2(2-py)] and W(:CHSiMe3)(CH2SiMe3)(:NPh)[OCPh2(2-py)]
  作者：Paul A. van der Schaaf、Robertus A. T. M. Abbenhuis、Walter P. A. van der Noort、Robin de Graaf、David M. Grove、Wilberth J. J. Smeets、Anthony L. Spek、Gerard van Koten

  DOI：10.1021/om00016a051

  日期：1994.4

  The lithium salts of selected phenoxides, with one or two potentially chelating o-CH2NMe2 substituents, 8-quinolinolate (8-quin), ortho-chelating arenethiolate ligands, and a-substituted 2-pyridylmethoxides, were reacted with W(CH2SiMe3)3Cl(=NPh) (1) and W(CH2SiMe3)2Cl-(=NPh)(OCMe3) (2), respectively. It appears that steric properties of the monoanionic O,N- and S,N-chelating ligands are very important for inducing an intramolecular H(alpha)-abstraction reaction; i.e., the phenoxide OC6H4CH2NMe2-2 (a) gave rise to the formation of alkylidene precursor W(CH2SiMe3)3(=NPh)(OC6H4CH2NMe2-2) (3), in which the alkyl groups are still intact, whereas the ''pincer phenolate'' OC6H2(CH2NMe2)2-2,6-Me-4 (b), with two o-CH2NMe2 substituents, directly led to the formation of alkylidene complex W(=CHSiMe3)(CH2SiMe3)(=NPh)(OC6H2(CH2NMe2)2-2,6-Me-4) (4'). The reaction of 1 with Na-8-quin instantaneously gave W(=CHSiMe3)(CH2SiMe3)(=NPh)(8-quin) (5'). Also, electronic properties play an important role in the formation of alkylidene complexes; i.e., the complexes derived from 2, containing a pi-electron-donating tert-butoxide group, are thermally more stable toward intramolecular H(alpha) abstraction than those derived from 1. With the alpha-substituted 2-pyridylmethoxide ligands OR1R2(2-py), in which the R substituents can be varied easily, we were able to prepare both the alkylidene precursor and the subsequent product of an intramolecular H(alpha)-abstraction reaction, the tungsten(VI) alkylidene complex. The solid-state structure (X-ray) of the trialkyltungsten(VI) precursor W(CH2SiMe3)3(=NPh)[OCPh2(2-py)] (9) as well as the resulting alkylidene complex W(=CHSiMe3)(CH2SiMe3)(=NPh)[OCPh2(2-py)] (9') have been determined. Crystals of 9 are monoclinic, space group P2(1)/c, with unit-cell dimensions a = 10.974(1) angstrom, b = 18.531(3) angstrom, and c = 20.307(2) angstrom, beta = 106.47(1)degrees, Z = 4, final R = 0.063, and R(w) = 0.053 for 2644 reflections with I > 2.5sigma(I) and 415 parameters. Crystals of 9' are triclinic, space group P1BAR, with unit-cell dimensions a = 9.4359(5) angstrom, b = 10-8887(7) angstrom, and c 16.611(1) alpha = 81.60(1)degrees, beta = 88.37(1)degrees, gamma = 79.19(1)degrees, Z=2, final R=0.042, and R(w) = 0.026 for 5879 reflections with I > 2.5sigma(I) and 348 parameters. The two molecular structures clearly show the advantage of a d0 metal center in forming an alkylidene unit out of two alkyl groups. The chemical shift of H-6, the hydrogen atom bonded at the ortho position with respect to the pyridyl nitrogen, as a probe shows that the pyridyl group in alkylidene complexes 9' and W(=CHSiMe3)(CH2SiMe3)(=NPh)[OCH(CMe3)(2-py)] (10') can coordinate intramolecularly in the syn rotamer, whereas in the anti rotamer this will lead to considerable steric hindrance of the SiMe3 group of the alkylidene function with the vicinal substituents in the chelating ring. The reactivity of the present tungsten(VI) alkylidene complexes 5', 9.', and 10' toward linear olefins is very low. However, aldehydes react with these complexes in Wittig-type reactions to yield predominantly the corresponding trans-olefin. Norbornene can be polymerized using these alkylidene complexes as a catalyst in a ring-opening metathesis reaction at 70-degrees-C to give polymeric cyclopentenes with greater-than-or-equal-to 90% cis vinylene bonds.
• Brandts, Jim A. M.; Boersma, Jaap; Spek, Anthony L., European Journal of Inorganic Chemistry, 1999, # 10, p. 1727 - 1733
  作者：Brandts, Jim A. M.、Boersma, Jaap、Spek, Anthony L.、Van Koten, Gerard

  DOI：——

  日期：——