Veauthier Jacqueline M, Cho Won-Seob, Lynch Vincent M, Sessler Jonathan L
Department of Chemistry and Biochemistry, 1 University Station--A5300, The University of Texas at Austin, Austin, Texas 78712-0165, USA.
Inorg Chem. 2004 Feb 23;43(4):1220-8. doi: 10.1021/ic0352001.
New bimetallic mu-oxo diferric complexes of several previously reported calix[4]pyrrole Schiff base macrocycles are described. The synthesis of a new member of this class of macrocycles is also reported; it was prepared via an acid-catalyzed condensation between 1,9-bisformyl-5,5-dipropyldipyrromethane and o-phenylenediamine. Reactions of the free base macrocycles or their bis-HCl salts with Fe(II) mesitylene, followed by air oxidation, gave the binuclear mu-oxo bis-Fe(III) compounds 6-10 in moderate yield. X-ray crystallography data reveal two different coordination environments for the Fe-O-Fe subunit in 6-10 that it is suggested can be controlled by altering the reaction conditions. Structural properties of these metalated pyrrolic macrocycles are also compared to those of mu-oxo diferric porphyrins and mu-oxo diferric texaphyrin. Complexes 6-10 exhibit two distinct types of M-N bonds that are similar in length to the bonds observed in metallotexaphyrin complexes. However, the electronics of the present systems are very different from those of texaphyrins and porphyrins in that no delocalized bonding patterns are observed within the ligands as a whole.
本文描述了几种先前报道的杯[4]吡咯席夫碱大环化合物的新型双金属μ-氧代二铁配合物。还报道了此类大环化合物新成员的合成；它是通过1,9-双甲酰基-5,5-二丙基二吡咯甲烷与邻苯二胺之间的酸催化缩合反应制备的。游离碱大环化合物或其二盐酸盐与二茂铁反应，随后进行空气氧化，以中等产率得到双核μ-氧代双铁(III)化合物6-10。X射线晶体学数据揭示了6-10中Fe-O-Fe亚基的两种不同配位环境，表明可以通过改变反应条件来控制。还将这些金属化吡咯大环化合物的结构性质与μ-氧代二铁卟啉和μ-氧代二铁 texaphyrin的结构性质进行了比较。配合物6-10表现出两种不同类型的M-N键，其长度与在金属texaphyrin配合物中观察到的键相似。然而，本体系的电子性质与texaphyrin和卟啉的电子性质非常不同，因为在整个配体中未观察到离域键合模式。
