邻位官能化的1,3 - 双（芳基）三氮烯基配体的双核钯（I）和钯（II）配合物
Binuclear palladium(I) and palladium(II) complexes of ortho-functionalized 1,3-bis(aryl)triazenido ligands.
作者信息
Nuricumbo-Escobar Juan José, Campos-Alvarado Carlos, Ríos-Moreno Gustavo, Morales-Morales David, Walsh Patrick J, Parra-Hake Miguel
机构信息
Centro de Graduados e Investigación, Instituto Tecnológico de Tijuana, Apartado Postal 1166, 22000 Tijuana, B. C. México.
出版信息
Inorg Chem. 2007 Jul 23;46(15):6182-9. doi: 10.1021/ic700516p. Epub 2007 Jun 20.
Three new bis(aryl)triazene ligands, Ar-NNNH-Ar' [Ar = o-C(6)H(4)-CO(2)Me, Ar' = p-C(6)H(4)-CH(3) (2); Ar = Ar' = o-C(6)H(4)-CO(2)Me (3); Ar = o-C(6)H(4)-SMe, Ar' = p-C(6)H(4)-CH(3)) (4)], have been synthesized. The reaction of 1-4 with PdCl(2)(NCCH(3))(2) in the presence of a base afforded a series of binuclear diamagnetic palladium complexes. In these reactions, ligands 1-3 afforded the palladium(I) complexes Pd(I)(o-MeO(2)C-C(6)H(4)-NNN-o-C(6)H(4)-CO(2)Me) (5, monoclinic, space group P21/c, a = 8.6070(10) Angstrom, b = 14.3220(10) Angstrom, c = 12.7310(10) Angstrom, beta = 100.2950(10) degrees, Z = 2), Pd(I)(o-MeO-C(6)H(4)-NNN-o-C(6)H(4)-OMe) (6, triclinic, space group P, a = 6.6288(5) Angstrom, b = 10.2631(10) Angstrom, c = 11.0246(11) Angstrom, alpha = 85.579(6) degrees, beta = 80.885(6) degrees, gamma = 74.607(6) degrees, Z = 1), and Pd(I)(o-MeO(2)C-C(6)H(4)-NNN-p-C(6)H(4)-CH(3)) (7, tetragonal, space group I41/a, a = 20.866(3) Angstrom, b = 20.866(3) Angstrom, c = 13.156(2) Angstrom, Z = 8). In contrast, the reaction of ligand 4 with PdCl(2)(NCCH(3))(2) resulted in the formation of a palladium(II) dimer, Pd(II)(o-MeS-C(6)H(4)-NNN-p-C(6)H(4)-CH(3))Cl (8, orthorhombic, space group P2(1)2(1)2, a = 10.4058(5) Angstrom, b = 16.2488(8) Angstrom, c = 9.9500(5) Angstrom, Z = 2).
合成了三种新型双（芳基）三氮烯配体，Ar-NNNH-Ar' [Ar = 邻 - C₆H₄ - CO₂Me，Ar' = 对 - C₆H₄ - CH₃ (2)；Ar = Ar' = 邻 - C₆H₄ - CO₂Me (3)；Ar = 邻 - C₆H₄ - SMe，Ar' = 对 - C₆H₄ - CH₃ (4)]。在碱存在下，1 - 4 与 PdCl₂(NCCH₃)₂反应得到了一系列双核抗磁性钯配合物。在这些反应中，配体 1 - 3 得到钯（I）配合物 [Pd(I)(邻 - MeO₂C - C₆H₄ - NNN - 邻 - C₆H₄ - CO₂Me)]₂ (5，单斜晶系，空间群 P21/c，a = 8.6070(10) Å，b = 14.3220(10) Å，c = 12.7310(10) Å，β = 100.2950(10)°，Z = 2)，[Pd(I)(邻 - MeO - C₆H₄ - NNN - 邻 - C₆H₄ - OMe)]₂ (6，三斜晶系，空间群 P，a = 6.6288(5) Å，b = 10.2631(10) Å，c = 11.0246(11) Å，α = 85.579(6)°，β = 80.885(6)°，γ = 74.607(6)°，Z = 1)，以及 [Pd(I)(邻 - MeO₂C - C₆H₄ - NNN - 对 - C₆H₄ - CH₃)]₂ (7，四方晶系，空间群 I41/a，a = 20.866(3) Å，b = 20.866(3) Å，c = 13.156(2) Å，Z = 8)。相比之下，配体 4 与 PdCl₂(NCCH₃)₂反应生成了钯（II）二聚体，[Pd(II)(邻 - MeS - C₆H₄ - NNN - 对 - C₆H₄ - CH₃)Cl]₂ (8，正交晶系，空间群 P2(1)2(1)2，a = 10.4058(5) Å，b = 16.2488(8) Å，c = 9.9500(5) Å，Z = 2)。
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