The Shrinking World of Innocent Ligands: Conventional and Non-Conventional Redox-Active Ligands
The Shrinking World of Innocent Ligands: Conventional and Non-Conventional Redox-Active Ligands
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DOI：
10.1002/ejic.201101359
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发表时间：
2012-01-01
影响因子：
2.3
通讯作者：
Kaim, Wolfgang
中科院分区：
文献类型：
--
作者：
Kaim, Wolfgang
这篇文章为EurJIC关于合作和氧化还原非无辜配体的集群问题向读者介绍了氧化还原活性配体，其范围从小的原型NO+/中心点/-和O-2（0/中心点-/2-）系统到经典的1，4-二杂-1，3-二烯螯合物（例如，G.α-二亚胺、二硫杂环戊烯或邻醌氧化还原系列）转化为π-共轭大环。配位化学中配体的氧化还原活性最近引起了越来越多的关注，现在已经促使更广泛的成功搜索，导致建立不太传统的例子，如氰化物，一氧化碳，硫醚，或乙酰丙酮衍生物作为非无害行为的配体。通过考虑具有显著共价金属-配体键合的情况，还将解决金属-氧代、金属-邻氨基和有机金属化合物的情况，并展望非无辜配体行为的普遍性。将指出氧化还原活性配体的材料和反应潜力。
This essay for EurJIC's cluster issue on cooperative and redox non-innocent ligands introduces the reader to redox-active ligands, which range from the small archetypical NO+/center dot/- and O-2(0/center dot-/2-) systems via the classical 1,4-dihetero-1,3-diene chelates (e. g. alpha-diimine, dithiolene, or o-quinone redox series) to pi-conjugated macrocycles. The increased attention paid recently to the redox activity of ligands in coordination chemistry has now prompted wider successful searches, resulting in the establishing of less-conventional examples such as cyanide, carbon monoxide, thioethers, or acetylacetonate derivatives as non-innocently behaving ligands. By considering situations with significantly covalent metal-ligand bonding, the cases of metal-oxo, metal-hydrido, and organometallic compounds will also be addressed, with a perspective on how pervasive non-innocent ligand behavior is. The materials and reactivity potential of redox-active ligands will be pointed out.