2,3,7,8,12,13,17,18-octaethylporphyrinato-ZrCl2 | 139166-68-0

• 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: 2,3,7,8,12,13,17,18-octaethylporphyrinato-ZrCl2
• 英文别名: dichloro(octaethylporphyrinato)zirconium(IV)；Zr(octaethylporphyrinate)Cl2；Zr(octaethylporphinate)Cl2
• CAS: 139166-68-0
• 化学式: C₃₆H₄₄Cl₂N₄Zr
• 分子量: 694.902
• InChiKey: NARPJMSOPSYOHQ-SBYLDBAISA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2,3,7,8,12,13,17,18-octaethylporphyrinato-ZrCl2 在 phenoxathiinylium hexachloroantimonate 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  锆（IV）和ha（IV）夹心卟啉配合物的光谱表征

  摘要：

  Optical, infrared (IR), and resonance Raman (RR) spectra are reported for the sandwich porphyrins Zr(OEP)2 and Hf(OEP)2 (OEP = octaethylporphyrin) and their respective mono- and dication radicals. For comparison, absorption and vibrational data were also obtained for representative neutral and oxidized monomeric Zr(IV) and Hf(IV) complexes. The vibrational data for both the monocations (all complexes) and dications (sandwich complexes only) indicate that the electrons are removed from an a1u-like molecular orbital. Consequently the ground states of the singly and doubly oxidized compounds are 2A1u and 1A1g, respectively. The C(b)C(b) stretching vibrations are found to be the most reliable indicators of oxidation. These modes exhibit almost linear upshifts upon successive oxidations of the porphyrin rings. On the basis of the shift-pattern exhibited by the IR oxidation-marker bands of the Zr(IV) and Hf(IV) species, the oxidation-marker band of MOEP complexes is identified as the nu38 (C(b)C(b)) stretching mode. In the course of the RR studies of the sandwich complexes, experiments were performed in which the excitation energy is resonant with the new electronic states that arise due to the strong pipi interactions in these assemblies. These include the Q' and Q'' states of the neutral species and the near-IR charge-resonance states of the cations. No RR scattering is observed upon excitation into either the Q' or Q'' absorptions. In contrast, excitation into the near-IR absorptions of the mono- and dications results in RR scattering from out-of-plane deformations of the porphyrin rings. The resonance enhanced out-of-plane deformations appear to be symmetrical linear combinations of porphyrin monomer vibrations rather than intradimer vibrations (modes that arise due to the additional degrees of freedom present in the dimer versus the two independent monomers). Collectively, the studies of the neutral and oxidized M(OEP)2 complexes provide further insights into the effects of strong pipi interactions and the consequences of ring-based oxidations in porphyrinic systems.

  DOI：

  10.1021/j100109a014
• 作为产物：
  描述：

  在 HCl 作用下， 以 氘代氯仿 为溶剂， 生成 2,3,7,8,12,13,17,18-octaethylporphyrinato-ZrCl2
  参考文献：
  名称：

  早期过渡金属卟啉：新颖的平面外顺式连接锆卟啉衍生物的合成，表征和反应性

  摘要：

  A new class of coordinatively unsaturated zirconium porphyrin compounds, (OEP)ZrR2 [OEP = dianion of octaethylporphyrin; R = chloride, trifluoromethanesulfonate (triflate, OTf), acetate, alkoxide, alkyl, aryl; R2 = cyclooctatetraenyl], has been prepared. (OEP)ZrCl2, prepared by metathesis between Li2OEP(DME)n and ZrCl4(DME), serves as starting material for further functionalization. The organometallic derivatives are very reactive, readily undergoing protonolysis, hydrogenolysis, and insertion of CO2 and acetone into the Zr-C bonds. Cis-ligation in these out-of-plane zirconium porphyrin compounds has been inferred from H-1 NMR measurements and confirmed in three derivatives by X-ray diffraction. Crystallographic data are as follows. (OEP)ZrCl2.0.5Tol: space group P1BAR with a = 9.870(2) angstrom, b = 14.143(3) angstrom, c = 14.498(3) angstrom, alpha = 66.257(17)-degrees, beta = 88.003(17)-degrees, gamma = 79.645(17)-degrees V = 1820.9(8) angstrom3, and Z = 2. (OEP)Zr(O(t)BU)2: space group P1BAR with a = 12.4441(12) angstrom, b = 13.1594(21) angstrom, c = 13.9541(18) angstrom alpha = 89.972(11)-degrees, beta = 99.192(9)-degrees, gamma = 115.487(11)-degrees V = 2045.7(10) angstrom3, and z = 2. (OEP)ZrMe2: space group P1BAR with a = 10.007(3) angstrom, b = 13.062(4) angstrom, c = 14.558(3) angstrom, alpha = 82.83(2)-degrees, beta = 88.24(2)-degrees, gamma = 79.98(2)-degrees, V = 1859.1(12) angstrom3, and Z = 2.

  DOI：

  10.1021/om00033a043

文献信息

• Novel low-valent zirconium porphyrin complexes: syntheses, characterization and X-ray crystal structures of (η5-cyclopentadienyl)zirconium tetraphenylporphyrin and (η2-diphenylacetylene)zirconium octaethylporphyrin
  作者：Hee-Joon Kim、Sungkyung Jung、You-Moon Jeon、Kimoon Kim

  DOI：10.1039/a705181f

  日期：——

  Reactions of (por)ZrCl2 [por = octaethylporphyrinato (oep) or tetraphenylporphyrinato (tpp) dianion] with TlCp and diphenylacetylene in the presence of Na/Hg or Mg produce novel low-valent zirconium porphyrin complexes (por)Zr(η5-Cp) 1 and (por)Zr(η2-PhCCPh) 2, respectively; spectroscopic and/or structural data for 1 and 2 are consistent with a formalism in which 1 is a resonance hybrid of a zirconium(III) metal-centered radical and a zirconium(IV) porphyrin radical anion while 2 is a zirconium(II) complex stabilized by a four-electron-donor alkyne ligand.

  (por)ZrCl2 [por = 八乙基卟啉 (oep) 或四苯基卟啉 (tpp) 二价阴离子] 与 TlCP 和二苯乙炔在 Na/Hg 或 Mg 存在下反应，生成新型低价锆卟啉配合物 (por)Zr(η5-分别为 CP) 1 和 (por)Zr(δ2-PhCCPh) 2 ； 1和2的光谱和/或结构数据与形式一致，其中1是锆(III)金属中心自由基和锆(IV)卟啉自由基阴离子的共振杂化物，而2是锆(II)络合物由四电子供体炔配体稳定。
• Novel η1-alkynyl zirconium porphyrin complexes: synthesis and characterization of (por)Zr(η1-CCR)3Li(THF) [por = octaethylporphyrinato (oep) or tetraphenylporphyrinato dianion (tpp); R = Ph, SiMe3]
  作者：Hee-Joon Kim、Sungkyung Jung、You-Moon Jeon、Dongmok Whang、Kimoon Kim

  DOI：10.1039/a901923e

  日期：——

  Reaction of (por)ZrCl2 [por = 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion (oep) or 5,10,15,20-tetraphenylporphyrinato dianion (tpp)] with 3 equiv. of LiCCR (R = Ph and SiMe3) produces novel alkynyl zirconium(IV) porphyrin complexes (por)Zr(η1-CCR)3Li(THF) in which three alkynyl ligands are coordinated to the zirconium center in a piano stool fashion and the Li+ ion is bound to the pocket formed by three alkynyl ligands; treatment of (por)Zr(η1-CCPh)3Li(THF) with anhydrous HCl produces a C–C bond coupled product H2CCPh(CCPh) and HCCPh quantitatively.

  (por)ZrCl2 [por = 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion (oep) or 5,10,15,20-tetraphenylporphyrinato dianion (tpp)]与 3 equiv.LiCCR（R = Ph 和 SiMe3）产生新型炔基锆(IV)卟啉配合物 (por)Zr(δ-1-CCR)3Li(THF) ，其中三个炔基配体以钢琴凳的方式配位到锆中心，Li+ 离子与三个炔基配体形成的口袋结合；用无水 HCl 处理 (por)Zr(δ-1-CCPh)3Li(THF) 可定量生成 CâC 键偶联产物 H2CCPh(CCPh) 和 HCCPh。
• Trioxygen-Bridged Porphyrin Dimers with Unusual Molecular Geometries. X-Ray Crystal Structures of {(μ-OH)₃[Zr(OEP)]₂}(7,8-C₂B₉H₁₂) and (μ-O)(μ-OH)₂[Zr(TPP)]₂
  作者：Hee-Joon Kim、Dongmok Whang、Youngkyu Do、Kimoon Kim

  DOI：10.1246/cl.1993.807

  日期：1993.5

  The X-ray structures of the title complexes revealed that the two zirconium porphyrin moieties are joined either by three bridging hydroxo ligands or by one oxo and two hydroxo ligands. In both structures, the two porphyrin macrocycles are perfectly or nearly eclipsed and concomitantly one of the Zr-O bonds eclipses one of the Zr-N bonds. Such unprecedented eclipsed conformation found in both structures strongly suggests that it is stabilized by dπ-pπ interactions between Zr and O and N atoms despite the unfavorable steric interactions.

  标题复合物的X射线结构显示，两个锆卟啉部分通过三个桥联羟基配体或一个氧配体和两个羟基配体连接。在这两种结构中，两个卟啉大环完全或几乎重叠，同时，一个Zr-O键与一个Zr-N键重叠。这两种结构中均存在这种前所未有的重叠构象，这有力地表明，尽管存在不利的空间相互作用，但Zr与O和N原子之间的dπ-pπ相互作用使该结构稳定。
• Zirconium(IV) Sandwich Complexes of Porphyrins and Tetraazaporphyrins:  Synthesis, Structure, and Nonlinear Optical Properties
  作者：James P. Collman、Jonathan L. Kendall、Judy L. Chen、Todd A. Eberspacher、Christopher R. Moylan

  DOI：10.1021/ic970657u

  日期：1997.11.1

  A family of bis(porphyrin) zirconium sandwich complexes containing octaethylporphyrin (OEP) and octaethyltetraazaporphyrin (OETAP) was synthesized and characterized by W-vis and NMR spectroscopies. The two ligands are structural analogues yet have dramatically different redox properties (the redox potentials of OETAP complexes are much more positive than those of the corresponding OEP complexes). Cyclic voltammetry results indicate that Zr(OETAP)(2) is about 600 mV harder to oxidize and about 600 mV easier to reduce than Zr(OEP)2, while the mixed sandwich Zr(OEP)(OETAP) exhibits intermediate redox potentials. The structures of Zr(OEP)(OETAP) and Zr(OETAP)2 were determined by X-ray crystallography and compared to Zr(OEP)(2). The solid state structures were very similar, indicating that OEP and OETAP have similar steric parameters and that observed spectroscopic and electrochemical differences are due primarily to electronic factors. The one electron oxidized porphyrin sandwiches were also synthesized. Characterization by W-vis, near-IR, EPR, and IR spectroscopies confirm the it radical nature of these complexes. IR spectra indicate that the cation is delocalized over the entire complex in both [Zr(OEP)(OETAP)](+)[SbCl6](-) and [Zr(OETAP)(2)](+)[SbCl6](-), consistent with a strongly coupled pi system. Additional evidence for strong coupling was obtained from measurement of the nonlinear optical properties of the mixed complex; the molecular hyperpolarizability is negative, indicating that the dipole moment reverses direction upon electronic excitation.
• Reaction of (POR)M(OAc)2 (M  Zr, Hf) with nBuLi and soild state structure of [(TPP)Zr(μ-OH)2]2
  作者：Jean L Huhmann、Joyce Y Corey、Nigam P Rath、Charles F Campana

  DOI：10.1016/0022-328x(95)05835-d

  日期：1996.5

  A general route to (TPP)Zr(OAc)(2), (OEP)Zr(OAc)(2) and (TPP)Hf(OAc)(2) from the reaction of MCl(4) and H-2(POR) in benzonitrile, followed by treatment with pyridine + acetic acid is described. The reaction of(POR)M(OAc)(2) with (n)BuLi occurs in a stepwise manner, with approximately 2 equiv. of (n)BuLi required before the formation of M((n)Bu) is observed, and 4 equiv. required for stoichiometric conversion to (POR)M((n)Bu)(2). The tetrahydroxo-bridged dimer [(TPP)Zr(mu-OH)(2)](2) was obtained as the benzene solvate from the hydrolysis of (TPP)Zr((n)Bu)(2), and the structure was determined by single crystal X-ray diffraction (triclinic, ; a=10.606(2) Angstrom,b=13.003(3) Angstrom, c=14.587(3) Angstrom, alpha=99.85(3)degrees, beta=107.61(3)degrees, gamma=96.82(3)degrees, Z=2).