3,8-二噻吩和3,8-二甲基噻吩-1,10-菲啰啉的锰(Ⅱ)和钴(Ⅱ)配合物的晶体结构、顺反异构及取代基效应研究 |
Synthesis, Crystal Structures, Cis-Trans Conformation and Substituent Effects of Manganese(Ⅱ) and Cobalt(Ⅱ) Complexes Having 3,8-Dithiophen or 3,8-Di-3-methylthiophen-1,10-phenanthroline |
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摘要: 本文报道了1个基于3,8-二噻吩-1,10-菲啰啉(dtphen) 的双核锰(Ⅱ)配合物1 [trans-Mn2Cl4(dtphen)2]和2个基于3,8-二甲基噻吩-1,10-菲啰啉(dmtphen)的单核锰(Ⅱ)和单核钴(Ⅱ)配合物2和3(分子式分别为[cis-MnCl2(dmtphen)2]和[cis-CoCl2(dmtphen)2])的合成、波谱和晶体结构表征.其中,2个锰(Ⅱ)配合物的分子结构呈现不同的配位模式,由于噻吩环上甲基引入所产生的位阻效应,导致单核配合物2和3中,两配体中的噻吩环相对于1,10-菲啰啉环呈现相同的反式/反式分子构型,其二面角分布在14.1(1)°~51.5(1)°.而对于双核配合物1,由于没有甲基位阻的影响,其相应芳环之间二面角减少至2.0(1)°~20.2(1)°,且配体呈现顺式/反式分子构型. |
关键词: 锰(Ⅱ)配合物 钴(Ⅱ)配合物 取代基效应 顺反异构 晶体结构 |
基金项目: 国家自然科学基金(No.21165013,21171088);中国博士后基金(No.2012M511720);江西省自然科学基金(No.2010GZH0112);南昌航空大学博士基金(No.EA201102327)资助项目. |
Abstract: A dinuclear 3,8-dithiophen substituted 1,10-phenanthroline (dtphen) manganese(Ⅱ) complex and a pair of 3,8-di-3-methylthiophen substituted 1,10-phenanthroline (dmtphen) manganese(Ⅱ) and cobalt(Ⅱ) complexes, formulated as [trans-Mn2Cl4(dtphen)2] (1), [cis-MnCl2(dmtphen)2] (2) and [cis-CoCl2(dmtphen)2] (3), were synthesized and characterized by elemental analysis, FTIR, UV-Vis spectra and X-ray single-crystal structural analysis. The two Mn(Ⅱ) complexes exhibit diverse coordination models in the whole molecular structures. In mononuclear complexe 2 and 3, both dmtphen ligands have similar trans/trans conformation but different dihedral angles ranging from 14.1(1)°~51.5(1)° because of the spatial crowding effects of methyl group. In contrast, the dihedral angles of dtphen ligands in dinuclear complex 1 are only within 2.0(1)°~20.2(1)° and the two side thiophene rings in the dtphen ligand adopt the cis/trans conformation relative to the central phen unit. CCDC: 870021, 1; 870022, 2; 870023, 3. |
Keywords: manganese(Ⅱ) complexe cobalt(Ⅱ) complexe substituent effects cis and trans configuration crystal structure |
投稿时间:2012-03-06 修订日期:2012-07-05 |
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胡斌,颜流水,张爱琴,黄伟.3,8-二噻吩和3,8-二甲基噻吩-1,10-菲啰啉的锰(Ⅱ)和钴(Ⅱ)配合物的晶体结构、顺反异构及取代基效应研究[J].无机化学学报,2012,28(12):2540-@. |
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