(κ3-(2-C5H4N)C(Me)(CH2NSiMe3)2)Ti(=NtBu)(py)

• 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: (κ3-(2-C5H4N)C(Me)(CH2NSiMe3)2)Ti(=NtBu)(py)
• 英文别名: Tert-butyliminotitanium(2+);(2-methyl-2-pyridin-2-yl-3-trimethylsilylazanidylpropyl)-trimethylsilylazanide;pyridine
• 化学式: C₂₄H₄₃N₅Si₂Ti
• 分子量: 505.69
• InChiKey: HHIYUUONUFAFSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.35
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (κ3-(2-C5H4N)C(Me)(CH2NSiMe3)2)Ti(=NtBu)(py) 在 B(C₆F₅)3 作用下， 以 氘代苯 为溶剂， 生成 [Ti(NtBu)(MeC(2-C5H4N)(CH2NSiMe3)2)]
  参考文献：
  名称：

  Group 4 Imido Complexes Stabilized by a Tridentate Diamido-Donor Ligand

  摘要：

  Reaction of the lithium amides [(2-C5H4N)C(CH3){CH2N(Li)SiMe3}(2)](2) (2a) and [(2-C5H4N)C(CH3){CH2N(Li)-SiMe(2)tBu}(2)](2) (2b) with the imidotransition metal complexes [Ti(NtBu)Cl-2(py)(3)], [Ti(N-2,6-C(6)H(3)iPr(2))Cl-2(py)(3)], and [Zr(N-2,6-C(6)H(3)iPr(2))Cl-2(thf)(2)] yielded the five-coordinate imido-titanium and -zirconium complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe2R)(2)}Ti(NR')(py)] (R = Me, R' = tBu: 3a, R = tBu, R' = tBu: 3b, R = Me, R' = 2,6-C(6)H(3)iPr(2): 4a, R = Me, R' = 2,6-C6H3Me2: 4b) and [(kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Zr(N-2,6-C(6)H(3)iPr(2))(py)] (5). The tridentate diamido-pyridine ligand adopts a facial coordination mode in the distorted trigonal bipyramidal complexes with the imido ligand occupying an equatorial position, as was established by X-ray diffraction for 3a and 5. Sublimation of 3a and 4a yielded the pure four-coordinate imidotitanium complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NR')] (R' = tBu: 6, 2,6-C(6)H(3)iPr(2): 7) which were structurally characterized by X-ray crystallography. Reaction of 3a with the Lewis acid B(C6F5)(3) also led to abstraction of the axially bound pyridine ligand and the formation of the adduct [py-B(C6F5)(3)] and 6. Reaction of 6 with thf, PMe3, and pyridine led to the formation of pentacoordinate complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}-Ti(NtBu)(thf)] (8), [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NtBu)(PMe3)] (9), and [{kappa N-3-(2-C5H4N)C(CH3)(CH2-NSiMe3)(2)}Ti(NtBu)(py)] (3a) in which the donor ligands occupy axial positions.

  DOI：

  10.1021/ic0005644
• 作为产物：
  描述：

  吡啶 、 [Ti(NtBu)(MeC(2-C5H4N)(CH2NSiMe3)2)] 以 氘代苯 为溶剂， 以99%的产率得到(κ3-(2-C5H4N)C(Me)(CH2NSiMe3)2)Ti(=NtBu)(py)
  参考文献：
  名称：

  Group 4 Imido Complexes Stabilized by a Tridentate Diamido-Donor Ligand

  摘要：

  Reaction of the lithium amides [(2-C5H4N)C(CH3){CH2N(Li)SiMe3}(2)](2) (2a) and [(2-C5H4N)C(CH3){CH2N(Li)-SiMe(2)tBu}(2)](2) (2b) with the imidotransition metal complexes [Ti(NtBu)Cl-2(py)(3)], [Ti(N-2,6-C(6)H(3)iPr(2))Cl-2(py)(3)], and [Zr(N-2,6-C(6)H(3)iPr(2))Cl-2(thf)(2)] yielded the five-coordinate imido-titanium and -zirconium complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe2R)(2)}Ti(NR')(py)] (R = Me, R' = tBu: 3a, R = tBu, R' = tBu: 3b, R = Me, R' = 2,6-C(6)H(3)iPr(2): 4a, R = Me, R' = 2,6-C6H3Me2: 4b) and [(kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Zr(N-2,6-C(6)H(3)iPr(2))(py)] (5). The tridentate diamido-pyridine ligand adopts a facial coordination mode in the distorted trigonal bipyramidal complexes with the imido ligand occupying an equatorial position, as was established by X-ray diffraction for 3a and 5. Sublimation of 3a and 4a yielded the pure four-coordinate imidotitanium complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NR')] (R' = tBu: 6, 2,6-C(6)H(3)iPr(2): 7) which were structurally characterized by X-ray crystallography. Reaction of 3a with the Lewis acid B(C6F5)(3) also led to abstraction of the axially bound pyridine ligand and the formation of the adduct [py-B(C6F5)(3)] and 6. Reaction of 6 with thf, PMe3, and pyridine led to the formation of pentacoordinate complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}-Ti(NtBu)(thf)] (8), [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NtBu)(PMe3)] (9), and [{kappa N-3-(2-C5H4N)C(CH3)(CH2-NSiMe3)(2)}Ti(NtBu)(py)] (3a) in which the donor ligands occupy axial positions.

  DOI：

  10.1021/ic0005644

文献信息

• C−C and C−N Coupling Reactions of an Imidotitanium Complex with Isocyanides
  作者：Allan Bashall、Philip E. Collier、Lutz H. Gade、Mary McPartlin、Philip Mountford、Stephen M. Pugh、Sanja Radojevic、Martin Schubart、Ian J. Scowen、Dominique J. M. Trösch

  DOI：10.1021/om0005710

  日期：2000.11.1

  imidoylketeneimene fragment to the metal center. The reaction of 1with alkyl isocyanides bearing H atoms α to the NC group leads to a sequential coupling of 3 molar equiv of the isocyanide with the imido complex, yielding metal-bonded diaminodihydropyrimidine derivatives (R = H, 4a; CH3, 4b; C3H7, 4c; Ph, 4d) and (R,R‘ = C5H10, 5a; CH3,CH3, 5b; Ph,CH3, 5c). An X-ray diffraction study of 4a unambiguously established

  所述imidotitanium复杂的反应[（κ 3 -N 2 NPY）的Ti（Ñ吨卜）（吡啶）]（1）[N 2 NPY细胞=（2-C 5 H ^ 4 N）C（Me）的（CH 2 NSiMe 3）2 ]与导致胩到imidotitanium键的重复插入和纯化，产生四元titanacycle 2,6- xylylisocyanide [（κ 3 -N 2 NPY）的Ti N（TBU）C（N-二2,6- Me 2 C 6 H 3）C（N-2,6-C 6 H 3 Me 2）}]（2），其通过X射线晶体学表征。2与大量的异氰酸酯R-NC [R = Et，n Bu，i Pr，Cy，t Bu，PhCH 2，p- Tol，（R）-CH（CH 3）Ph ]，得到iminoketene配合物[（κ 3 -N 2 NPY）的Ti N（吨卜）C [N（2,6--ME 2 ç 6 ħ 3）] C（ç NR）N（2
• Highly selective trimerisation of MeNC by a novel titanium imido complex containing a tridentate dianionic ligand
  作者：Alexander J. Blake、Philip E. Collier、Lutz H. Gade、Mary McPartlin、Philip Mountford、Martin Schubart、Ian J. Scowen

  DOI：10.1039/a703275g

  日期：——

  A new type of imido compound [Ti(NBu t )L(py)] 1 containing a tripodal dianionic ligand is reported which effects the remarkably selective trimerisation of MeNC; the crystal structures of 1 and [TiLN(Me)N(Bu t )(C 4 H 3 N 2 M e)}] 2 are described [L = MeC(2-C 5 H 4 N)(CH 2 NSiMe 3 ) 2 ].

  一种新型亚氨基化合物[Ti(NBu t )L(py)] 1 包含 据报道，三足双阴离子配体显着影响 MeNC 的选择性三聚化； 1 和 的晶体结构 [TiLN(Me)N(Bu t )(C 4 H 3 氮 2 中号 e)}] 2 被描述为 [L = MeC(2-C 5 H 4 N)(CH 2 氮硅镁 3 ） 2 ]。
• Group 4 Imido Complexes Stabilized by a Tridentate Diamido-Donor Ligand
  作者：Alexander J. Blake、Philip E. Collier、Lutz H. Gade、Philip Mountford、Julian Lloyd、Stephen M. Pugh、Martin Schubart、Michael E. G. Skinner、Dominique J. M. Trösch

  DOI：10.1021/ic0005644

  日期：2001.2.1

  Reaction of the lithium amides [(2-C5H4N)C(CH3)CH2N(Li)SiMe3}(2)](2) (2a) and [(2-C5H4N)C(CH3)CH2N(Li)-SiMe(2)tBu}(2)](2) (2b) with the imidotransition metal complexes [Ti(NtBu)Cl-2(py)(3)], [Ti(N-2,6-C(6)H(3)iPr(2))Cl-2(py)(3)], and [Zr(N-2,6-C(6)H(3)iPr(2))Cl-2(thf)(2)] yielded the five-coordinate imido-titanium and -zirconium complexes [kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe2R)(2)}Ti(NR')(py)] (R = Me, R' = tBu: 3a, R = tBu, R' = tBu: 3b, R = Me, R' = 2,6-C(6)H(3)iPr(2): 4a, R = Me, R' = 2,6-C6H3Me2: 4b) and [(kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Zr(N-2,6-C(6)H(3)iPr(2))(py)] (5). The tridentate diamido-pyridine ligand adopts a facial coordination mode in the distorted trigonal bipyramidal complexes with the imido ligand occupying an equatorial position, as was established by X-ray diffraction for 3a and 5. Sublimation of 3a and 4a yielded the pure four-coordinate imidotitanium complexes [kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NR')] (R' = tBu: 6, 2,6-C(6)H(3)iPr(2): 7) which were structurally characterized by X-ray crystallography. Reaction of 3a with the Lewis acid B(C6F5)(3) also led to abstraction of the axially bound pyridine ligand and the formation of the adduct [py-B(C6F5)(3)] and 6. Reaction of 6 with thf, PMe3, and pyridine led to the formation of pentacoordinate complexes [kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}-Ti(NtBu)(thf)] (8), [kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NtBu)(PMe3)] (9), and [kappa N-3-(2-C5H4N)C(CH3)(CH2-NSiMe3)(2)}Ti(NtBu)(py)] (3a) in which the donor ligands occupy axial positions.