Metal-Induced Thiophene Ring Opening and C-C Bond Formation To Produce Unique Hexa-1,3,5-trienediyl-Coupled Non-Innocent Ligand Chelates.
Metal-Induced Thiophene Ring Opening and C-C Bond Formation To Produce Unique Hexa-1,3,5-trienediyl-Coupled Non-Innocent Ligand Chelates.
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DOI：
10.1002/chem.201502748
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发表时间：
2015-10
期刊：
影响因子：
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通讯作者：
Fabian Ehret;Martina Bubrin;S. Záliš;J. L. Priego;R. Jiménez-Aparicio;W. Kaim
中科院分区：
文献类型：
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作者：
Fabian Ehret;Martina Bubrin;S. Záliš;J. L. Priego;R. Jiménez-Aparicio;W. Kaim
在噻吩与[Ru（acac）2（CH 3CN）2 ]（acac=乙酰丙酮）反应时，观察到2位含偶氮官能团的噻吩开环，然后通过C-C偶联二聚，生成两个1，3，5-己三烯连接的氧化还原活性偶氮硫代羰基螯合物体系。通过磁性和电子光谱测量结合DFT计算研究了非无辜螯合配体和金属在纳米级距离为1.45 nm处通过共轭己三烯桥的相互作用，揭示了这种独特设置的四中心磁性相互作用和还原后的弱价间耦合。
Ring opening of thiophenes containing an azo function in 2-position and subsequent dimerization through C-C coupling were observed on reaction with [Ru(acac)2 (CH3 CN)2 ] (acac=acetylacetonate) to produce two 1,3,5-hexatriene-linked redox-active azothiocarbonyl chelate systems. Interaction of the non-innocent chelate ligands and of the metals at a nanoscale distance of 1.45 nm via the conjugated hexatriene bridge was studied by magnetic and electron spectroscopic measurements in conjunction with DFT calculations, revealing four-center magnetic interactions of this unique setting and weak intervalence coupling after reduction.