Rhodium and Palladium Complexes of NHeterocyclic Olefin (NHO) Ligand Fused with the 9,10-Dihydro-9,10-ethanoanthracene Framework
Rhodium and Palladium Complexes of NHeterocyclic Olefin (NHO) Ligand Fused with the 9,10-Dihydro-9,10-ethanoanthracene Framework
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与 9,10-二氢-9,10-乙蒽骨架稠合的 NHO 杂环烯烃 (NHO) 配体的铑和钯配合物
DOI：
10.1021/acs.organomet.1c00503
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发表时间：
2021
期刊：
影响因子：
2.8
通讯作者：
Tadao Ishizuka
中科院分区：
文献类型：
--
作者：
Shin Ando;Akio Ohara;Tomohiko Ohwada;Tadao Ishizuka
通过2-亚甲基咪唑烷与9，10-二氢-9，10-乙蒽骨架的稠合，合成了一种饱和型的N-杂环烯烃（NHO），并成功地合成了该NHO的铑、钯配合物。用Rh配合物计算的Tolman电子参数（TEP）表明，饱和NHO的给电子能力弱于不饱和NHO。X射线衍射（XRD）研究表明，三种钯配合物分别为[（NHO）PdCl（μ-Cl）]2，trans-[（NHO）2 PdCl 2]，cis-[（NHO）2 PdCl 2]，trans-[（NHO）2 PdCl 2]在乙腈溶液中异构化为酸配合物。此外，我们的计算研究表明，N-取代基是至关重要的平面性的2-亚甲基咪唑烷部分，我们的NHO及其金属配合物。
A saturated type of N-heterocyclic olefin (NHO) was synthesized by fusing 2-methyleneimidazolidine with a 9,10-dihydro-9,10-ethanoanthracene framework, and rhodium and palladium complexes with this NHO were successfully obtained. The Tolman electronic parameter (TEP) value calculated using the Rh complex indicated that the electron-donating ability of the present saturated NHO was weaker than those of unsaturated NHOs. X-ray diffraction (XRD) studies of three Pd complexes confirmed that these complexes were [(NHO)PdCl(μ-Cl)]2,trans-[(NHO)2PdCl2], andcis-[(NHO)2PdCl2].trans-[(NHO)2PdCl2] isomerized to acis-complex in an acetonitrile solution. Furthermore, our computational studies indicated that the N-substituent is crucial for the planarity of the 2-methyleneimidazolidine moiety of our NHO and its metal complexes.