Metal complexes from 1,1'-di(pyrazinyl)ferrocene: coordination polymers and bridged diferrocenes.
Metal complexes from 1,1'-di(pyrazinyl)ferrocene: coordination polymers and bridged diferrocenes.
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DOI：
10.1039/b511286a
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发表时间：
2006-01
影响因子：
4
通讯作者：
T. Mochida;K. Okazawa;R. Horikoshi
中科院分区：
文献类型：
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作者：
T. Mochida;K. Okazawa;R. Horikoshi
合成了二茂铁基配体1，1 '-二（吡嗪基）二茂铁（L1）和1，1'-二（2-嘧啶基）二茂铁（L2），并由L1合成了铜和银配合物。配位聚合物[{Cu（2）（PhCOO）（4）}（L1）]（n）（1）、[{Cu（2）（C（5）H（11）COO）（4）}（L1）]（n）（2）和[{Cu（2）（OAc）（4）}（L1）]（n）.0.5n[Cu（2）（OAc）（4）（H（2）O）（2）].1.5nCH（3）CN（3）由相应的羧酸铜反应得到。在所有三种配合物中，L1连接双核铜羧酸盐单元形成一维阶梯状链。在2中，这些链进一步通过[Cu（2）（OAc）（4）（H（2）O）（2）]双核单元通过氢键连接以形成片状结构。L1与碘化铜（I）反应生成多核配合物[（CuI）（4）（L1）（2）]。(L1)（4），它含有一个具有阶梯状（CuI）（4）核的[（CuI）（4）（L1）（2）]双二茂铁单元。L1与银（I）盐反应生成银桥联双二茂铁[Ag（2）（L1）（2）]X（2）（X = ClO（4）（5a，B），NO（3）（6a-c）和PF（6）（7）），其中一些化合物在晶格中引入了芳香溶剂。分子内Ag…银在这些金属大环（3.211-3.430）的分离取决于抗衡阴离子和银离子的配位模式。在所有这些配合物中，L1采用同面重叠构象，并作为一个双齿配体，只有每个吡嗪环的5-氮参与协调。
Ferrocene-based ligands 1,1'-di(pyrazinyl)ferrocene (L1) and 1,1'-di(2-pyrimidinyl)ferrocene (L2) were synthesized and copper and silver complexes were obtained from L1. Coordination polymers [{Cu(2)(PhCOO)(4)}(L1)](n) (1), [{Cu(2)(C(5)H(11)COO)(4)}(L1)](n) (2), and [{Cu(2)(OAc)(4)}(L1)](n).0.5n[Cu(2)(OAc)(4)(H(2)O)(2)].1.5nCH(3)CN (3) resulted from the reaction with the corresponding copper carboxylates. In all three complexes, L1 links the dinuclear copper carboxylate units to form one-dimensional step-like chains. In 2, these chains are further linked by [Cu(2)(OAc)(4)(H(2)O)(2)] dinuclear units via hydrogen bonding to form sheet structures. The reaction of L1 with copper(I) iodide resulted in a multinuclear complex [(CuI)(4)(L1)(2)].(L1) (4), which contains a [(CuI)(4)(L1)(2)] diferrocene unit with a step-like (CuI)(4) core. Reactions of L1 with silver(I) salts resulted in silver-bridged diferrocenes [Ag(2)(L1)(2)]X(2) (X = ClO(4) (5a, b), NO(3) (6a-c) and PF(6) (7)), some of which incorporate aromatic solvents into their crystal lattices. The intramolecular Ag...Ag separations in these metallamacrocycles (3.211-3.430 A) depended upon the counter-anions and on the coordination mode of the silver ions. In all of these coordination complexes, L1adopts a synperiplanar eclipsed conformation and acts as a bidentate ligand, with only the 5-nitrogen of each pyrazine ring involved in coordination.