[Hf(meso-tetra-p-tolylporphyrin)Cl2] | 189344-22-7

• 英文名称: [Hf(meso-tetra-p-tolylporphyrin)Cl2]
• CAS: 189344-22-7
• 化学式: C₄₈H₃₆Cl₂HfN₄
• 分子量: 918.237
• InChiKey: SBRVZWMGZVWECN-KDTBAHQYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  lithium p-toluidinate 、 [Hf(meso-tetra-p-tolylporphyrin)Cl2] 以 further solvent(s) 为溶剂， 以59%的产率得到(meso-tetra-p-tolylporphyrinato)Hf(NHC6H4-p-Me)2
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of Zirconium and Hafnium Imido Metalloporphyrins

  摘要：

  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)).

  DOI：

  10.1021/ic981399j

文献信息

• Synthesis, Characterization, and Reactivity of Group 4 Metalloporphyrin Diolate Complexes
  作者：Guodong Du、L. Keith Woo

  DOI：10.1021/om020790g

  日期：2003.2.1

  A number of group 4 metalloporphyrin diolate complexes were synthesized via various approaches. For example, treatment of imido complex (TTP)HfNAriPr with diols resulted in formation of the corresponding diolato complexes (TTP)Hf[OCR1R2CR1R2O] (R1 = R2 = Me, 1; R1 = Me, R2 = Ph, 2; R1 = R2 = Ph, 3). Treatment of (TTP)TiNiPr with diols generated (TTP)Ti[OCR1R2CR1R2O] (R1 = R2 = Me, 5; R1 = Me, R2 =

  通过各种方法合成了许多第4族金属卟啉二醇酸酯复合物。例如，用二醇处理亚胺基络合物（TTP）Hf NAr iPr导致形成相应的二醇基络合物（TTP）Hf [OCR 1 R 2 CR 1 R 2 O]（R 1 = R 2 = Me，1 ; R 1 = Me，R 2 = Ph，2； R 1 = R 2 = Ph，3）。用生成的二醇（TTP）Ti [OCR 1 R 2 CR 1处理（TTP）Ti N i PrR 2 O]（R 1＝ R 2＝ Me，5； R 1＝ Me，R 2＝ Ph，6； R 1＝ H，R 2＝ Ph，7； R 1＝ H，R 2＝对甲苯基，8）。或者，通过（TTP）MCl 2（M = Hf，Ti）与松果酸二钠的复分解反应制备pin酸钛和pin酸钛1和5。complex配合物的取代化学与二醇基配体的碱性密切相关。配合1 - 6进行氧化裂解反应，生成羰基化合物和金属氧卟啉。对于较少取