| 168331-69-9

• CAS: 168331-69-9
• 化学式: C₃₇H₅₁N₄Nb
• 分子量: 644.745
• InChiKey: PAUUURGOAZAWCL-UHFFFAOYSA-N

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：

  、 一氧化碳 以 甲苯 为溶剂， 以81%的产率得到(C₄H₂N)3(C₅H₂NCH₃)(C(CH₂CH₃)2)4NbO
  参考文献：
  名称：

  Macrocyclic Modification Using Organometallic Methodologies. Regiochemically Controlled Mono- and Bis-Homologation Reactions of Porphyrinogen with Carbon Monoxide Assisted by Early Transition Metals

  摘要：

  The homologation of a pyrrole to a pyridine ring within the porphyrinogen skeleton was achieved with high selectivity, good yield, and controlled regiochemistry and was scaled up to multiple gram quantities. The homologation of meso-octaethylporphyrinogen to meso-octaethyltris(pyrrole)-monopyridine was carried out by reacting carbon monoxide with Zr-C and Zr-H functionalities supported by the meso-octaethylporphyrinogen ligand [Et(8)N(4)H(4)]. The starting materials [(eta(5)-eta(1)-eta(5)-eta(1)-Et(8)N(4))Zr(mu-NaH)](2) (2) and [(eta(5)-eta(1)-eta(5)-eta(1)-Et(8)N(4))Zr(mu-KH)](2) (3) have been obtained by a direct addition of alkali hydrides to [(eta(5)-eta(1)-eta(5)-eta(1)-Et(8)N(4))Zr(THF)] (1) or via hydrozirconation reactions in the cases of [{(eta(5)-eta(1)-eta(1)-eta(1)-Et(8)N(4))ZrCH2CH3}(2)(mu-K)(2)] (6) and [{(eta(5)-eta(1)-eta(1)-eta(1)-Et(8)N(4))ZrCH=CH2}(2)(mu-K)(2)] (7). The reaction of 3 with carbon monoxide led to the intermediate formation of an eta(2)-formyl group possessing significant carbenium ion character, which was displayed in its addition to a pyrrole unit to give a pyridine ring in [{(eta(5)-eta-(1) eta-(5) eta-(1)Et(8)-(C4H2N)(3)C5H3N)Zr= O)(2)(mu-K)(2)] (4) The overall result is the formation of a novel macrocycle containing three pyrroles and one pyridine unit binding a zirconyl fragment derived from a complete cleavage of a C-O multiple bond. A straightforward hydrolysis of 4 with H2O gave a high yield of the free macrocycle [Et(8)(C4H2NH)(3)(C5H3N)] (5). The carbonylation of 6 and 7 allowed the determination of the regiochemistry of the homologation reaction which gave, upon hydrolysis of the corresponding zirconyl complex, the following free macrocycles [Et(8)(C4H2NH)(3)(3-RC(5)H(2)N)] [R = CH2CH3, 8; R = CH=CH2, 9]. The intermediate eta(2)-acyl homologates one of the pyrroles to a m-alkylpyridine ring. By this methodology we are able to introduce functionalizable substituents into the pyridine ring, i.e., in 9. General procedures are reported for one-pot large-scale synthesis of free trispyrrole-monopyridine macrocycles. The reaction of [(eta(5)-)eta(1)-eta(1)-eta(1)-Et(8)N(4))Nb-Me] (12) with carbon monoxide led to the oxoniobium(V) complex [{eta(5)-eta(1)-eta(1)-eta(1)-Et(8)(C4H2N)(3)(p-MeC(5)H(2)N)}Nb=O] (13) due to the carbenium ion properties of the intermediate eta(2)-acetyl derivative. Complex 13 contains the meso-octaethyltrispyrrole-monopyridine trianion derived from the homologation of one of the pyrrole rings of [Et(8)N(4)H(4)] into p-methylpyridine. The formation of a para-substituted pyridine is ascribed to the eta(3) bonding mode of one of the pyrrolyl anions.The homologation of the trispyrrole-monopyridine macrocycle [Et(8)(C4H2NH)(3)(C5H3N)] (7) to the bispyrrole-bispyridine macrocycle has been achieved using a sequence which involves the key hafnium derivative [{eta(5)-eta(1)-eta(5)-eta(1)-Et(8)(C4H2N)(3)(C5H3N)}Hf-Me] (17). The reaction of 17 with carbon monoxide provides the homologation of a further pyrrolyl anion into m-methylpyridine, giving the cis-bispyridine-bispyrrole macrocycle binding the oxohafnium(IV) unit in [cis-Et(8)(C4H2N)(3)(C5H3N)(m-MeC(5)H(2)N)Hf=O] (18). The hydrolysis of 18 freed the ligand [Et(8)(C4H2NH)(2)(C5H3N)(m-MeC(5)H(2)N)] (19) which was characterized by an X-ray analysis. Crystallographic details: compound 8 is triclinic, space group P $($) over bar$$ 1, a = 13.763(3) Angstrom, b = 14.464(2) Angstrom, c = 19.276(3) Angstrom, alpha = 82.77(1)degrees, beta = 89.71(2)degrees, gamma = 76.52(1)degrees, Z = 2, and R = 0.045. Compound 13 is monoclinic, space group C2/c, a = 29.380(5) Angstrom, b = 13.367(4) Angstrom, c = 40.862(7) Angstrom, alpha = gamma = 90 degrees, beta = 107.55(2)degrees, Z = 16, and R = 0.047. Compound 17 is monoclinic, space group P2(1)/n, a = 11.459(3) Angstrom, b = 13.140(3) Angstrom, c = 23.454(4) Angstrom, alpha = gamma = 90 degrees, beta = 102.23(3) Angstrom, Z = 4, and R = 0.026. Compound 19 is monoclinic, space group P2(1)/n, a = 13.038(3) Angstrom, b = 18.859(3) Angstrom, c = 14.805(3) Angstrom, alpha = gamma = 90 degrees, beta = 102.80(2)degrees, Z = 4, and R = 0.057.

  DOI：

  10.1021/ja00115a014
• 作为产物：
  描述：

  [(η(5):η(1):η(5):η(1)-Et4(C4H2N)4)NbCl] 、 甲基锂 以 甲苯 为溶剂， 以67%的产率得到
  参考文献：
  名称：

  Macrocyclic Modification Using Organometallic Methodologies. Regiochemically Controlled Mono- and Bis-Homologation Reactions of Porphyrinogen with Carbon Monoxide Assisted by Early Transition Metals

  摘要：

  The homologation of a pyrrole to a pyridine ring within the porphyrinogen skeleton was achieved with high selectivity, good yield, and controlled regiochemistry and was scaled up to multiple gram quantities. The homologation of meso-octaethylporphyrinogen to meso-octaethyltris(pyrrole)-monopyridine was carried out by reacting carbon monoxide with Zr-C and Zr-H functionalities supported by the meso-octaethylporphyrinogen ligand [Et(8)N(4)H(4)]. The starting materials [(eta(5)-eta(1)-eta(5)-eta(1)-Et(8)N(4))Zr(mu-NaH)](2) (2) and [(eta(5)-eta(1)-eta(5)-eta(1)-Et(8)N(4))Zr(mu-KH)](2) (3) have been obtained by a direct addition of alkali hydrides to [(eta(5)-eta(1)-eta(5)-eta(1)-Et(8)N(4))Zr(THF)] (1) or via hydrozirconation reactions in the cases of [{(eta(5)-eta(1)-eta(1)-eta(1)-Et(8)N(4))ZrCH2CH3}(2)(mu-K)(2)] (6) and [{(eta(5)-eta(1)-eta(1)-eta(1)-Et(8)N(4))ZrCH=CH2}(2)(mu-K)(2)] (7). The reaction of 3 with carbon monoxide led to the intermediate formation of an eta(2)-formyl group possessing significant carbenium ion character, which was displayed in its addition to a pyrrole unit to give a pyridine ring in [{(eta(5)-eta-(1) eta-(5) eta-(1)Et(8)-(C4H2N)(3)C5H3N)Zr= O)(2)(mu-K)(2)] (4) The overall result is the formation of a novel macrocycle containing three pyrroles and one pyridine unit binding a zirconyl fragment derived from a complete cleavage of a C-O multiple bond. A straightforward hydrolysis of 4 with H2O gave a high yield of the free macrocycle [Et(8)(C4H2NH)(3)(C5H3N)] (5). The carbonylation of 6 and 7 allowed the determination of the regiochemistry of the homologation reaction which gave, upon hydrolysis of the corresponding zirconyl complex, the following free macrocycles [Et(8)(C4H2NH)(3)(3-RC(5)H(2)N)] [R = CH2CH3, 8; R = CH=CH2, 9]. The intermediate eta(2)-acyl homologates one of the pyrroles to a m-alkylpyridine ring. By this methodology we are able to introduce functionalizable substituents into the pyridine ring, i.e., in 9. General procedures are reported for one-pot large-scale synthesis of free trispyrrole-monopyridine macrocycles. The reaction of [(eta(5)-)eta(1)-eta(1)-eta(1)-Et(8)N(4))Nb-Me] (12) with carbon monoxide led to the oxoniobium(V) complex [{eta(5)-eta(1)-eta(1)-eta(1)-Et(8)(C4H2N)(3)(p-MeC(5)H(2)N)}Nb=O] (13) due to the carbenium ion properties of the intermediate eta(2)-acetyl derivative. Complex 13 contains the meso-octaethyltrispyrrole-monopyridine trianion derived from the homologation of one of the pyrrole rings of [Et(8)N(4)H(4)] into p-methylpyridine. The formation of a para-substituted pyridine is ascribed to the eta(3) bonding mode of one of the pyrrolyl anions.The homologation of the trispyrrole-monopyridine macrocycle [Et(8)(C4H2NH)(3)(C5H3N)] (7) to the bispyrrole-bispyridine macrocycle has been achieved using a sequence which involves the key hafnium derivative [{eta(5)-eta(1)-eta(5)-eta(1)-Et(8)(C4H2N)(3)(C5H3N)}Hf-Me] (17). The reaction of 17 with carbon monoxide provides the homologation of a further pyrrolyl anion into m-methylpyridine, giving the cis-bispyridine-bispyrrole macrocycle binding the oxohafnium(IV) unit in [cis-Et(8)(C4H2N)(3)(C5H3N)(m-MeC(5)H(2)N)Hf=O] (18). The hydrolysis of 18 freed the ligand [Et(8)(C4H2NH)(2)(C5H3N)(m-MeC(5)H(2)N)] (19) which was characterized by an X-ray analysis. Crystallographic details: compound 8 is triclinic, space group P $($) over bar$$ 1, a = 13.763(3) Angstrom, b = 14.464(2) Angstrom, c = 19.276(3) Angstrom, alpha = 82.77(1)degrees, beta = 89.71(2)degrees, gamma = 76.52(1)degrees, Z = 2, and R = 0.045. Compound 13 is monoclinic, space group C2/c, a = 29.380(5) Angstrom, b = 13.367(4) Angstrom, c = 40.862(7) Angstrom, alpha = gamma = 90 degrees, beta = 107.55(2)degrees, Z = 16, and R = 0.047. Compound 17 is monoclinic, space group P2(1)/n, a = 11.459(3) Angstrom, b = 13.140(3) Angstrom, c = 23.454(4) Angstrom, alpha = gamma = 90 degrees, beta = 102.23(3) Angstrom, Z = 4, and R = 0.026. Compound 19 is monoclinic, space group P2(1)/n, a = 13.038(3) Angstrom, b = 18.859(3) Angstrom, c = 14.805(3) Angstrom, alpha = gamma = 90 degrees, beta = 102.80(2)degrees, Z = 4, and R = 0.057.

  DOI：

  10.1021/ja00115a014

文献信息

• Niobium−Carbon Functionalities Supported by <i>meso</i>-Octaethylporphyrinogen and Derived Macrocycles
  作者：Sylviane Isoz、Carlo Floriani、Kurt Schenk、Angiola Chiesi-Villa、Corrado Rizzoli

  DOI：10.1021/om950537z

  日期：1996.1.9

  This report concerns the organometallic chemistry of niobium based on a macrocyclic ligand. To this purpose, the (meso- octaalkylporphyrinogen)niobium(V) complex [(eta(5): eta(1):eta(5):eta(1)-Et(8)N(4))-NbCl], 2, has been used as an appropriate starting material. The ionization of the Nb-Cl bond by the use of AgSO3CF3 gave a bifunctional acid-base system with an increased acidity of the metal center in [(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Nb(THF)O3SCF3)], 3. The alkylation of 2 with LiMe gave a quite stable Nb(V) organometallic derivative [(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Nb-Me] 4, which undergoes a migratory insertion reaction with Bu(t)NC leading to an eta(2)-iminoacyl derivative [(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Nb(Bu(t)NC)(eta(2)-C(Me)=NBu(t))], 6 (nu(C=N)) 2217 and 1736 cm(-1)). Two steps. of the reaction have been identified. An attempt to functionalize the Nb=O in [(eta(5):eta(1):eta(1):eta(1)-Et(8)(C4H2N)(3)(p-MeC(5)H(2)N)Nb=O], 7, by the use of LiMe led, on the contrary, to [(eta(1):eta(1):eta(1):eta(1)- Et(7)(CH-Me)(C4H2N)(3)(p-MeC(5)H(2)N)NbOLi(THF)(3)] derived from the metalation of one of the meso-ethyl groups in 9. While X-ray analysis provided information on the solid state structures of 3, 4, 6, and 9, NMR studies allowed us to establish a relationship between the bonding mode of the porphyrinogen in the solid state and in solution.