Tetrachloro-(4-methylphenyl)iminotungsten | 111053-11-3

• 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: Tetrachloro-(4-methylphenyl)iminotungsten
• CAS: 111053-11-3
• 化学式: C₇H₇Cl₄NW
• 分子量: 430.801
• InChiKey: IHBJLPWMHMSLLR-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Tetrachloro-(4-methylphenyl)iminotungsten 在 四氢呋喃 作用下， 以 四氢呋喃 为溶剂， 生成 {WCl4(NC6H4CH3-4)(thf)}
  参考文献：
  名称：

  Nitrogen nuclear magnetic resonance spectroscopy as a probe of bonding, bending and fluxionality of the imido ligand

  摘要：

  Nitrogen-14 and -15 NMR studies of imido (NR)-ligands have been made for 37 complexes of Ta, Mo, W, Re and Os, including bent NR ligands, with evidence of bent-linear fluxionality in solution, in concert with an OR or a second NR ligand. A striking difference from diazenido (N=NR) or nitrosyl ligands is the small difference in nitrogen shift for linear and bent NR ligands, the latter appearing across the whole range for NR ligands of the metals studied (with R = H, Me, Et, Bu(t), CH2But, aryl or SiMe3) in complexes with co-ordination numbers ranging from four to seven, and OR, Cl, F, NHR, NR2, N(SiMe3)2, S2CNEt2, phosphine, diphosphine or oxo coligands. This range, delta(N), -90 to 156, resembles that of linear ligating nitrogen in N2 and NO ligands; the shielding is higher than in nitrides, with low-energy n(N) --> pi* paramagnetic circulations, and lower than in bridging imides and amides. The deshielding on bending is much smaller than for N=NR or NO ligands because the imido lowest-unoccupied molecular orbitals (LUMOs), mainly pi*(MN) and sigma*(MN), are higher-lying than the pi*(NN) and pi*(NO) LUMOs. Another difference in the imido ligand is the closer parallelism of the nitrogen and the metal shielding, both of which increase with (sigma + pi)-acceptor ability of the coligands (increasing the ligand-field splitting). In the [WCl4(NC6H4X-4)(thf)] (thf = tetrahydrofuran) series, similarly, the nitrogen shielding increases in the sequence X = OMe < Me < H < F < Cl < NO2, with increase in (sigma + pi)-acceptor ability of the aromatic group. The overall pattern of imido-nitrogen shielding, including the periodicity of the metal dependence (the shielding increasing down the group of the metal, but decreasing across the row) thus resembles that of other pi-donor ligands such as oxo and fluoro but differs from that of pi-acceptor nitrogen ligands, such as N2, N=NR or NO.

  DOI：

  10.1039/dt9920001663
• 作为产物：
  描述：

  tungsten(VI) oxychloride 、 对甲苯异氰酸酯 以 苯 为溶剂， 生成 Tetrachloro-(4-methylphenyl)iminotungsten
  参考文献：
  名称：

  Nitrogen nuclear magnetic resonance spectroscopy as a probe of bonding, bending and fluxionality of the imido ligand

  摘要：

  Nitrogen-14 and -15 NMR studies of imido (NR)-ligands have been made for 37 complexes of Ta, Mo, W, Re and Os, including bent NR ligands, with evidence of bent-linear fluxionality in solution, in concert with an OR or a second NR ligand. A striking difference from diazenido (N=NR) or nitrosyl ligands is the small difference in nitrogen shift for linear and bent NR ligands, the latter appearing across the whole range for NR ligands of the metals studied (with R = H, Me, Et, Bu(t), CH2But, aryl or SiMe3) in complexes with co-ordination numbers ranging from four to seven, and OR, Cl, F, NHR, NR2, N(SiMe3)2, S2CNEt2, phosphine, diphosphine or oxo coligands. This range, delta(N), -90 to 156, resembles that of linear ligating nitrogen in N2 and NO ligands; the shielding is higher than in nitrides, with low-energy n(N) --> pi* paramagnetic circulations, and lower than in bridging imides and amides. The deshielding on bending is much smaller than for N=NR or NO ligands because the imido lowest-unoccupied molecular orbitals (LUMOs), mainly pi*(MN) and sigma*(MN), are higher-lying than the pi*(NN) and pi*(NO) LUMOs. Another difference in the imido ligand is the closer parallelism of the nitrogen and the metal shielding, both of which increase with (sigma + pi)-acceptor ability of the coligands (increasing the ligand-field splitting). In the [WCl4(NC6H4X-4)(thf)] (thf = tetrahydrofuran) series, similarly, the nitrogen shielding increases in the sequence X = OMe < Me < H < F < Cl < NO2, with increase in (sigma + pi)-acceptor ability of the aromatic group. The overall pattern of imido-nitrogen shielding, including the periodicity of the metal dependence (the shielding increasing down the group of the metal, but decreasing across the row) thus resembles that of other pi-donor ligands such as oxo and fluoro but differs from that of pi-acceptor nitrogen ligands, such as N2, N=NR or NO.

  DOI：

  10.1039/dt9920001663

文献信息

• Nitrogen-to-Metal Multiple Bond Functionalities:  The Reaction of Calix[4]arene−W(IV) with Azides and Diazoalkanes
  作者：Geoffroy Guillemot、Euro Solari、Carlo Floriani、Corrado Rizzoli

  DOI：10.1021/om000612s

  日期：2001.2.1

  [calix[4]-(O)4}W(η2-C6H10)], 2, has been used as a source of WIV-d2 center-bonded to an oxo surface, which has been modeled by the calix[4]arene tetraanion in the reaction with diazoalkanes and organic azides. The olefin is easily displaced by both substrates. The reaction with Ph2CN2 led to the formation of metallahydrazone, [calix[4]-(O)4}WN−NCPh2], 5, which binds ButNC inside the cavity, 6, or it can be reduced

  的[杯[4] - （O）4 } W（η 2 -C 6 H ^ 10）]，2，已被用作W的源IV -d 2中心键合到羰基合成表面，这一直由杯[4]芳烃四阴离子在与重氮烷烃和有机叠氮化物的反应中模拟。烯烃容易被两种底物取代。与pH值反应2 CN 2导致metallahydrazone的形成，[杯[4] - （O）4 } W的N- NCPH 2 ]，5，其结合卜吨NC腔内，6，或者它可以是减少为双核W V衍生物[W-W，2.646（1）]，其中，所述两个金属通过一个diphenylhydrazido配体中复杂的桥7，[杯[4] - （O）4 } 2 w ^ 2 μ-N-N（器CPh 2）2 Na 2 ]。2与有机叠氮化物（RN 3）的反应在很大程度上取决于R取代基在叠氮化物官能度上的性质。与RN 3的反应[R = SiMe 3 ; 器CPh 3 ]发生在外型位置的金属，导致alkylimido衍生物[杯[4]
• Ashcroft, Barry R.; Nielson, Alstair J.; Bradley, Donald C., Journal of the Chemical Society, Dalton Transactions, 1987, p. 2059 - 2066
  作者：Ashcroft, Barry R.、Nielson, Alstair J.、Bradley, Donald C.、Errington, R. John、Hursthouse, Michael B.、Short, Richard L.

  DOI：——

  日期：——