Tasiopoulos Anastasios J, Perlepes Spyros P
Department of Chemistry, University of Cyprus, 1678, Nicosia, Cyprus.
Dalton Trans. 2008 Nov 7(41):5537-55. doi: 10.1039/b805014g. Epub 2008 Jul 31.
The combination of diol-type ligands with paramagnetic transition metal ions has led to the isolation of a host of new homometallic and heterometallic clusters, high-spin molecules and single molecule magnets ranging in nuclearity from two to forty four and with spin ground states as large as S = 61/2. The ligands, whose cluster coordination chemistry is discussed in this article, are 1,3-propanediol and its derivatives, diethanolamine and its derivatives, pyridine-2,6-dimethanol and the gem-diol form of di-2-pyridyl ketone. The structural diversity of the complexes stems from the ability of the ligands to adopt a variety of bridging coordination modes depending on the positions of the two hydroxyl groups in the molecule, the presence/absence of extra donor groups and on the reaction conditions. Examples of 'true' reactivity chemistry involving clusters of diol-type ligands are also given. The activation of pyridine-2,6-dimethanol and di-2-pyridyl ketone by 3d-metal centres towards further reactions seems to be an emergent area of synthetic chemistry.
二醇型配体与顺磁性过渡金属离子的结合，已促使人们分离出大量新型同核和异核簇合物、高自旋分子以及单分子磁体，其核数范围从二到四十四，自旋基态高达(S = 61/2)。本文讨论了其簇合物配位化学的配体包括1,3 - 丙二醇及其衍生物、二乙醇胺及其衍生物、吡啶 - 2,6 - 二甲醇以及二 - 2 - 吡啶基酮的偕二醇形式。配合物的结构多样性源于配体根据分子中两个羟基的位置、额外供体基团的存在与否以及反应条件采取多种桥连配位模式的能力。文中还给出了涉及二醇型配体簇合物的“真正”反应化学的实例。3d金属中心对吡啶 - 2,6 - 二甲醇和二 - 2 - 吡啶基酮的活化以促进进一步反应，似乎是合成化学中一个新兴的领域。
