β,β'-稠合金属茂卟啉的合成、表征及电化学研究

Synthesis, characterization, and electrochemical studies of beta,beta'-fused metallocenoporphyrins.

作者信息

Wang Hong J H, Jaquinod Laurent, Olmstead Marilyn M, Vicente M Graça H, Kadish Karl M, Ou Zhongping, Smith Kevin M

机构信息

Department of Chemistry, University of California, Davis, California 95616, USA.

出版信息

Inorg Chem. 2007 Apr 2;46(7):2898-913. doi: 10.1021/ic062303l. Epub 2007 Feb 27.

DOI:10.1021/ic062303l

PMID:17323945

Abstract

Beta,beta'-Fused monoruthenocenylporphyrins, Cp*Ru(III)[1,2-[M(II)-5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)-porphyrinato]-3-methyl-cyclopentadienide] (M = Ni (20), Cu (21), Zn (22)), and bisferrocenoporphyrins, Fe(II) bis[1,2-[M(II)-5,10,15,20-tetraphenylporphyrinato]-3-methyl-cyclopentadienide] (M = Ni (24), Cu (25), Zn (26)), were synthesized and characterized. A novel synthetic approach to beta,beta'-fused porphyrins through Pd(0)-catalyzed [3 + 2] cycloaddition was implemented in this work. UV-vis spectra of these compounds show largely broadened and red-shifted bands (relative to their precursors) indicating potential electronic communication between the attached organometallic moiety and the porphyrin core. The electrochemistry of these molecules suggests significant electronic interactions between the metallocene and metalloporphyrin in molecules 20 and 24. The crystal structure of the bisferrocenoporphyrin 26, Fe(II) bis[1,2-[Zn(II)-5,10,15,20-tetraphenylporphyrinato]-3-methyl-cyclopentadienide], was determined: [Cp2Fe[ZnTPP(THF)]2][Cp2Fe[ZnTPP(THF)ZnTPP(MeOH)]].3MeOH.6THF, M = 3804.35, monoclinic, space group P21/c, a = 33.327(5) A, b = 19.145(3) A, c = 29.603(5) A, beta = 106.309(2) degrees , V = 18128(5) A3, Z = 4. In this molecule, one porphyrin ring is rotated by about 72 degrees with respect to the other in the 5-fold axis of the Cp ring.

摘要

β,β'-稠合单钌茂基卟啉，即Cp*Ru(III)[1,2-[M(II)-5,10,15,20-四(3,5-二叔丁基苯基)-卟啉基]-3-甲基-环戊二烯基]（M = Ni (20)、Cu (21)、Zn (22)）以及双二茂铁基卟啉，即Fe(II)双[1,2-[M(II)-5,10,15,20-四苯基卟啉基]-3-甲基-环戊二烯基]（M = Ni (24)、Cu (25)、Zn (26)），已被合成并表征。本工作采用了一种通过钯(0)催化的[3 + 2]环加成反应合成β,β'-稠合卟啉的新方法。这些化合物的紫外可见光谱显示出谱带大幅变宽且红移（相对于其前体），这表明所连接的有机金属部分与卟啉核心之间存在潜在的电子通讯。这些分子的电化学性质表明分子20和24中的二茂铁与金属卟啉之间存在显著的电子相互作用。已测定双二茂铁基卟啉26，即Fe(II)双[1,2-[Zn(II)-5,10,15,20-四苯基卟啉基]-3-甲基-环戊二烯基]的晶体结构：[Cp2Fe[ZnTPP(THF)]2][Cp2Fe[ZnTPP(THF)ZnTPP(MeOH)]].3MeOH.6THF，M = 3804.35，单斜晶系，空间群P21/c，a = 33.327(5) Å，b = 19.145(3) Å，c = 29.603(5) Å，β = 106.309(2)°，V = 18128(5) Å3，Z = 4。在该分子中，一个卟啉环相对于另一个在Cp环的5重轴上旋转了约72°。