Synthesis and magnetic properties of manganese carbonyl complexes with different coordination modes of 3,4,5-triaryl-1,2-diphospholide ligands.
Synthesis and magnetic properties of manganese carbonyl complexes with different coordination modes of 3,4,5-triaryl-1,2-diphospholide ligands.
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DOI：
10.1039/c5dt00624d
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发表时间：
2015-05
影响因子：
4
通讯作者：
V. Miluykov;I. Bezkishko;L. Kochetkova;O. Kataeva;T. Gerasimova;S. Katsyuba;O. Sinyashin;P. Lönnecke;E. Hey‐Hawkins;Anupama Parameswaran;Y. Krupskaya;V. Kataev;B. Büchner
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文献类型：
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作者：
V. Miluykov;I. Bezkishko;L. Kochetkova;O. Kataeva;T. Gerasimova;S. Katsyuba;O. Sinyashin;P. Lönnecke;E. Hey‐Hawkins;Anupama Parameswaran;Y. Krupskaya;V. Kataev;B. Büchner
配合物组 bis-(μ:η(1),η(1)-3,4,5-triaryl-1,2-diphosphacyclopentadienyl)-bis-(tetracarbonyl manganese(i)) (aryl = C6H5 (), p-FC6H4 (), p-ClC6H4 ()) 经历不可逆重排形成单核3,4,5-三芳基-1,2-二磷杂萁烯()。根据量子化学计算，双核配合物可以被认为是动力学控制的产物，而单核物质是热力学上有利的化合物。观察到的配合物的反铁磁分子内相互作用可以通过使用芳环对位的取代基来有效调节，而单核 1,2-二磷酸萁烯是抗磁性的。
The set of complexes bis-(μ:η(1),η(1)-3,4,5-triaryl-1,2-diphosphacyclopentadienyl)-bis-(tetracarbonyl manganese(i)) (aryl = C6H5 (), p-FC6H4 (), p-ClC6H4 ()) undergo an irreversible rearrangement to mononuclear 3,4,5-triaryl-1,2-diphosphacymantrenes (). According to quantum-chemical calculations binuclear complexes can be considered to be products of kinetic control and mononuclear species are thermodynamically favorable compounds. The antiferromagnetic intramolecular interaction observed for complexes can be effectively tuned by using substituents in the para-position of the arene ring, whereas mononuclear 1,2-diphosphacymantrenes are diamagnetic.