Zr(N(2,6-diisopropylphenyl))Cl2(THF)2 | 142839-73-4

• 英文名称: Zr(N(2,6-diisopropylphenyl))Cl2(THF)2
• 英文别名: Zr(2,6-(i-Pr)2C6H3N)Cl2(THF)2；[Zr(N-2,6-C6H3(i)Pr2)Cl2(tetrahydrofuran)2]
• CAS: 142839-73-4
• 化学式: C₂₀H₃₃Cl₂NO₂Zr
• 分子量: 481.618
• InChiKey: ZIJFGBRCGAOYAO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  1,3,5-三甲基己羟基-1,3,5-三嗪 、 Zr(N(2,6-diisopropylphenyl))Cl2(THF)2 以 二氯甲烷-D2 为溶剂， 以>99的产率得到ZrCl2(2,6-(i-Pr)2C6H3N)(1,3,5-trimethyl-1,3,5-triazacyclohexane)
  参考文献：
  名称：

  Titanium imido complexes containing 1,3,5-triazacyclohexane ligands

  摘要：

  The syntheses of the 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R'(3)tach)Cl-2] (M = Ti or Zr (NMR only); R = Bu-t or 2,6-C6H3Pr'(2); R' = Me or Bu-t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBut)(Me(3)tach)(CH2Ph)(2)]. The tert-butylimido ligand in [Ti(NBut)(Me(3)tach)Cl-2] undergoes exchange with ArNH2 (Ar = 4-C6H3Me or 2,6-C6H3Pr'(2)) to form the corresponding arylimides [Ti(NAr)(Me(3)tach)Cl-2]. The Me(3)tach ring in [Ti(NR)(Me(3)tach)Cl-2] undergoes slow exchange with Bu(3)(t)tach or Me(3)tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu(3)(t)tach)Cl-2] and [Ti(NR)(Me(3)tacn)Cl-2], respectively. The complexes [Ti(NR)(Me(3)tach)X-2] (R = Bu-t or 2,6-C6H3Pr2i; X = Cl or CH2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me(3)tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu(3)(t)tach)Cl-2] (R = Bu-t or 2,6-C6H3Pr2i) and [Ti(NBut)(Me(3)tach)(X)(2)] (X = Cl or CH2Ph) are reported. Me(3)tach and Bu(3)(t)tach = 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane, respectively. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00032-2

文献信息

• Synthesis, Structure, and Reactivity of Zirconium and Hafnium Imido Metalloporphyrins
  作者：Joseph L. Thorman、Ilia A. Guzei、Victor G. Young,、L. Keith Woo

  DOI：10.1021/ic981399j

  日期：1999.8.1

  The zirconium and hafnium porphyrin imido complexes (TTP)M = NAriPr [TTP = meso-tetra-p-tolylporphyrinato dianion, M = Zr (1), Hf (2), Ar-iPr = 2,6-diisopropylphenyl] were synthesized from (TTP)MCl2 and 2 equiv of LiNHAriPr. The zirconium imido complex, (TTP)Zr=NAriPr, was also obtained from the preformed imido complex Zr(NAriPr)Cl-2(THF)(2) and (TTP)Li-2(THF)(2). Treatment of (TTP)HfCl2 with excess LiNH(p-MeC6H4) resulted in the formation of a bis(amido) complex, (TTP)Hf(NH-p-MeC6H4)(2) (3), instead of an imido complex. In the presence of excess aniline, 2 formed an equilibrium mixture of bis(amido) compounds, (TTP)Hf(NHPh)(NHAriPr) and (TTP)Hf(NHPh)(2). The nucleophilic character of the imido moiety is exhibited by its reaction with (BuNCO)-Bu-t, producing isolable N,O-bound ureato metallacycles. The kinetic product obtained with zirconium, (TTP)Zr(eta(2)-(NArC)-C-iPr(=(NBu)-Bu-t)O) (4a), isomerized to (TTP)Zr(eta(2)-(NBuC)-Bu-t(=NAriPr)O) (4b) in solution. Upon being heated to 80 degrees C, 3a produced the carbodiimide (ArN)-N-iPr=C=(NBu)-Bu-t and a transient Zr(IV) oxo complex. The analogous hafnium complex (TTP)Hf(eta(2)-(NArC)-C-iPr(=(NBu)-Bu-t)O) (5a) did not eject the carbodiimide upon heating to 110 degrees C but isomerized to (TTP)Hf(eta(2)-(NBuC)-Bu-t(=NAriPr)O) (5b). To support the formulation of 4a and 5a as N,O bound, the complex (TTP)Hf(eta(2)-(NArC)-C-iPr(=NAriPr)O) (6) was studied by variable-temperature NMR spectroscopy. The corresponding thio- and selenoureato metallacycles were not isolable in the reaction between 1 and 2 with (BuNCS)-Bu-t and (BuNCSe)-Bu-t. Concomitant formation of the metallacycle with decomposition to the carbodiimide, (ArN)-N-iPr=C=(NBu)-Bu-t, reflects the lower C-Ch bond strength in the proposed N,Ch-bound metallacycles. Treatment of 2 with 1,3-diisopropylcarbodiimide resulted in the eta(2)-guanidino complex (TTP)Hf(eta(2)-(NArC)-C-iPr(=(NPr)-Pr-i)(NPr)-Pr-i) (7a), which isomerized to the less sterically crowded isomer (TTP)Hf(eta(2)-(NPrC)-Pr-i(=NAriPr)(NPr)-Pr-i) (7b). Complexes 1, 2, 4a, 4b, and 7a were characterized by X-ray crystallography. The monomeric terminal imido compounds, 1 and 2, are isomorphous: M-N-imido distances of 1.863(2) Angstrom (Zr) and 1.859(2) Angstrom (Hf); M-N-imido-C angles of 172.5(2)degrees (Zr) and 173.4(2)degrees (Hf). The structures of the ureato complexes 4a and Ib and the guanidino complex 7a exhibit typical alkoxido and amido bond distances (Zr-N = 2.1096(13) Angstrom (ils), 2.137(3) Angstrom (4b); Zr-O = 2.0677(12) Angstrom (4a). 2.066(3) Angstrom (4b); Hf-N 2.087(2) Angstrom, 2.151(2) Angstrom (7a)).
• 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.