1-(aquapalladium)-2,6-bis[(3,5-dimethylpyrazol-1-yl)methyl]benzene tetrafluoroborate | 353795-53-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(aquapalladium)-2,6-bis[(3,5-dimethylpyrazol-1-yl)methyl]benzene tetrafluoroborate
• 英文别名: 1-[[3-[(3,5-dimethylpyrazol-1-yl)methyl]benzene-2-id-1-yl]methyl]-3,5-dimethylpyrazole;palladium(2+);tetrafluoroborate;hydrate
• CAS: 353795-53-6
• 化学式: BF₄*C₁₈H₂₃N₄OPd
• 分子量: 504.631
• InChiKey: IPKJTPFOVOASBI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.6
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  α,α'-bis(3,5-dimethylpyrazolyl)-m-xylene 以 水 、 溶剂黄146 、 丙酮 为溶剂， 生成 1-(aquapalladium)-2,6-bis[(3,5-dimethylpyrazol-1-yl)methyl]benzene tetrafluoroborate
  参考文献：
  名称：

  Design and Performance of Rigid Nanosize Multimetallic Cartwheel Pincer Compounds as Lewis-Acid Catalysts

  摘要：

  Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous catalysts in a nanomembrane reactor. The ligand precursors C-6[C6H3(CH2Y)(2)-3,5](6) (10, Y= NMe2; 11, Y = SPh; 12, Y = PPh2; 13, Y = pz = pyrazol-1-yl) have been prepared in high yields from the key intermediate C-6[C6H3(CH2Br)(2)-3,5](6) (9). The hexakis(pincer) palladium(II) complexes C-6[(PdX)-4-C2H2(CH2Y)(2)-3,5](6) (14, Y = SPh, L = Cl; 15, Y = PPh2, L = Cl; 16, Y = pyrazol-1-yl, L = OAc; 17, Y = pyrazol-1-yl, L = Cl) have been prepared via direct electrophilic palladation of the corresponding ligands. The (tris)pincer ligand C6H3 [Br-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (20) was prepared via a triple-condensation reaction of 4-bromo-3,5-bis [(dimethylamino)methyl] acetophenone (19). Reaction of 20 with Pd(dba)(2) yielded the tripalladium complex C6H3[(PdBr)-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (21). The crystal structure of 21 shows a propeller-like structure with D-3 symmetry and a fixed bromine-bromine distance of 17.4573(4) Angstrom, approximately forming a triangle with a height of 15.2 Angstrom. These nanosize cartwheel pincer metal complexes based on tridentate Y,C,Y ' pincer ligands have been used as homogeneous Lewis-acid catalysts. Moreover, the influence of the donor substituent Y on the catalytic activity of cationic mono-Y,C,Y ' Pd-II complexes as Lewis-acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl a-cyanoacetate, as a model reaction, has been investigated. It was found that cationic N,C,N ' -type pincer complexes (1a, Y = NMe2; 1b, Y = pz; 1c, Y = pz* = 3,5-dimethylpyrazol-1-yl; 23) were superior to the P,C,P '- and S,C,S'-pincer complexes (Id, Y = PPh2; le, Y = SPh). The nanosize cationic tri-N, C,N ' Pd-II complex 23 was found to have a catalytic activity per catalytic site in the double Michael reaction of the same order of magnitude as the monopincer analogue 1a (k = 279 x 10(-6) s(-1) for 1a vs k = 232 x 10(-6) s(-1) for 23). The combination of the nanosize dimensions, the catalytic activity, and the high thermal and air stability makes these complexes excellent candidates for application in a continuous process in a nanomembrane reactor.

  DOI：

  10.1021/om0101689

文献信息

• Design and Performance of Rigid Nanosize Multimetallic Cartwheel Pincer Compounds as Lewis-Acid Catalysts
  作者：Harm P. Dijkstra、Michel D. Meijer、Jim Patel、Rob Kreiter、Gerard P. M. van Klink、Martin Lutz、Anthony L. Spek、Allan J. Canty、Gerard van Koten

  DOI：10.1021/om0101689

  日期：2001.7.1

  Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous catalysts in a nanomembrane reactor. The ligand precursors C-6[C6H3(CH2Y)(2)-3,5](6) (10, Y= NMe2; 11, Y = SPh; 12, Y = PPh2; 13, Y = pz = pyrazol-1-yl) have been prepared in high yields from the key intermediate C-6[C6H3(CH2Br)(2)-3,5](6) (9). The hexakis(pincer) palladium(II) complexes C-6[(PdX)-4-C2H2(CH2Y)(2)-3,5](6) (14, Y = SPh, L = Cl; 15, Y = PPh2, L = Cl; 16, Y = pyrazol-1-yl, L = OAc; 17, Y = pyrazol-1-yl, L = Cl) have been prepared via direct electrophilic palladation of the corresponding ligands. The (tris)pincer ligand C6H3 [Br-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (20) was prepared via a triple-condensation reaction of 4-bromo-3,5-bis [(dimethylamino)methyl] acetophenone (19). Reaction of 20 with Pd(dba)(2) yielded the tripalladium complex C6H3[(PdBr)-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (21). The crystal structure of 21 shows a propeller-like structure with D-3 symmetry and a fixed bromine-bromine distance of 17.4573(4) Angstrom, approximately forming a triangle with a height of 15.2 Angstrom. These nanosize cartwheel pincer metal complexes based on tridentate Y,C,Y ' pincer ligands have been used as homogeneous Lewis-acid catalysts. Moreover, the influence of the donor substituent Y on the catalytic activity of cationic mono-Y,C,Y ' Pd-II complexes as Lewis-acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl a-cyanoacetate, as a model reaction, has been investigated. It was found that cationic N,C,N ' -type pincer complexes (1a, Y = NMe2; 1b, Y = pz; 1c, Y = pz* = 3,5-dimethylpyrazol-1-yl; 23) were superior to the P,C,P '- and S,C,S'-pincer complexes (Id, Y = PPh2; le, Y = SPh). The nanosize cationic tri-N, C,N ' Pd-II complex 23 was found to have a catalytic activity per catalytic site in the double Michael reaction of the same order of magnitude as the monopincer analogue 1a (k = 279 x 10(-6) s(-1) for 1a vs k = 232 x 10(-6) s(-1) for 23). The combination of the nanosize dimensions, the catalytic activity, and the high thermal and air stability makes these complexes excellent candidates for application in a continuous process in a nanomembrane reactor.