Setsune Ji Jun-ichiro, Takeda Hirokazu, Ito Shoji, Saito Yugo, Ishimaru Yoshihiro, Fukuhara Koji, Saito Yasushi, Kitao Teijiro, Adachi Tomohiro
Department of Chemistry, Faculty of Science, Kobe University, Nada, Kobe 657, Japan, and Department of Applied Chemistry, College of Engineering, and Department of Chemistry, School of Integrated Arts and Sciences, University of Osaka Prefecture, Sakai, Osaka 591, Japan.
Inorg Chem. 1998 May 4;37(9):2235-2246. doi: 10.1021/ic970770k.
The nucleophilic addition reaction of a pyrrole nitrogen of free-base porphyrins to a pi-complexed acetylene ligand in a cationic Co(III) porphyrin intermediate afforded good yields of vinylene-Co,N'-linked bis(porphyrin)s, (Por)Co(III)-CH=CH-(N-Por)H(2). N-substituted porphyrin free bases are N-vinylated regioselectively at the pyrrole adjacent to the original N-substituted pyrrole in this reaction. Tris- and tetrakis(porphyrin)s have been prepared by reacting a vinylene-N,N'-linked bis(meso-tetraarylporphyrin) with (OEP)Co(III)(H(2)O)(2)ClO(4) (OEP: octaethylporphyrin dianion) and acetylene. The tetrakis(porphyrin) proved to be a 1:1 mixture of C(i)()- and C(2)-symmetric regioisomers. These organometallic Co(III) complexes underwent facile oxidative migration of the Co-bound vinyl group to a porphyrin pyrrole nitrogen when treated with Fe(III) salts or HClO(4) to provide moderate to good yields of Co(II) vinylene-N,N'-linked multi(porphyrin) complexes. (Vinylene-N,N')bis(porphyrin) free bases with combinations of different porphyrins have been obtained by this procedure. The homobinuclear (2Co(II), 2Cu(II), and 2Zn(II)) and heterobinuclear (Co(II)Cu(II) and Co(II)Zn(II)) complexes have been prepared and characterized spectroscopically. The single-crystal X-ray analysis of (CH=CH-N,N')[(OEP)Co(II)Cl][(TPP)Zn(II)Cl] (TPP: meso-tetraphenylporphyrin dianion) showed a face-to-face structure with an average inter-ring separation of 4.39 Å (triclinic P&onemacr;; Z = 2; a = 14.806(4), b = 18.703(10), c = 13.796(3) Å, alpha = 97.69(3), beta = 99.57(2), gamma = 96.74(3) degrees ).
在阳离子钴（III）卟啉中间体中，游离碱卟啉的吡咯氮对π-络合乙炔配体的亲核加成反应，以良好的产率得到了亚乙烯基 - 钴，N'-连接的双（卟啉）化合物，(Por)Co(III)-CH=CH-(N-Por)H₂。在此反应中，N-取代的卟啉游离碱在与原始N-取代吡咯相邻的吡咯处进行区域选择性N-乙烯基化。通过使亚乙烯基 - N，N'-连接的双（中位 - 四芳基卟啉）与(OEP)Co(III)(H₂O)₂ClO₄（OEP：八乙基卟啉二价阴离子）和乙炔反应，制备了三（卟啉）和四（卟啉）化合物。四（卟啉）被证明是Cᵢ-对称和C₂-对称区域异构体的1:1混合物。当用铁（III）盐或高氯酸处理时，这些有机金属钴（III）配合物的钴结合乙烯基容易发生氧化迁移至卟啉吡咯氮，以中等至良好的产率提供钴（II）亚乙烯基 - N，N'-连接的多（卟啉）配合物。通过此方法获得了具有不同卟啉组合的（亚乙烯基 - N，N'）双（卟啉）游离碱。制备了同双核（2Co（II）、2Cu（II）和2Zn（II））和异双核（Co（II）Cu（II）和Co（II）Zn（II））配合物，并通过光谱进行了表征。(CH=CH-N,N')[(OEP)Co(II)Cl][(TPP)Zn(II)Cl]（TPP：中位 - 四苯基卟啉二价阴离子）的单晶X射线分析显示出面对面结构，平均环间距为4.39 Å（三斜晶系P&onemacr;；Z = 2；a = 14.806(4)，b = 18.703(10)，c = 13.796(3) Å，α = 97.69(3)，β = 99.57(2)，γ = 96.74(3)°）。
