联吡啶四氮唑单核钆(Ⅲ)配合物的甲基化影响（英文）

Effect of the Methylation on Mononuclear Gd(Ⅲ) Bipyridyl Tetrazolate Complexes

应用6-(氢-5-四氮唑基)-2,2′-联吡啶(tbpy H)和6-(氢-5-四氮唑基)-4,4′-二甲基-2,2′-联吡啶(tmbpyH)配体,合成得到2个新的单核钆(Ⅲ)配合物[Gd(tbpy)_2(DMF)(H_2O)_2]NO_3·2H_2O(1)和[Gd(tmbpy)_2(DMF)(NO_3)]·DMF·THF(2)。X射线单晶衍射表明,每个钆(Ⅲ)离子均表现为1个畸变的三冠三角棱柱体,包含了2个四氮唑基N-H去质子化而产生的一价阴离子三齿螯合配体。此外,在2,2′-联吡啶环上引入2个甲基对钆(Ⅲ)金属中心的配位环境有显著影响,表现为2个单齿配位的水分子被1个螯合配位的硝酸根离子取代。

Two new mononuclear Gd （Ⅲ）complexes,[Gd （tbpy）2 （DMF） （H2O）2]NO3·2H2O （1）and[Gd （tmbpy）2 （DMF） （NO3）]·DMF·THF （2）, have been synthesized by using 6-（1H-tetrazole-5-yl）-2,2＇-bipyridyle （tbpyH）and 6-（1H-tetrazole-5-yl）-4,4＇-dimethyl-2,2＇-bipyridyle （tmbpyH）. As revealed by single-crystal X-ray diffraction, each Gd （Ⅲ）ion has a distorted tricapped trigonal prism with two mono-anionic tridentate chelating ligands, originating from N-H deprotonation of the tetrazolyl ring, and the introduction of two methyl groups into the 2,2＇-bypridyl ring has a significant effect on the coordination environment of the Gd （Ⅲ）core, showing that two mono-coordinated H2O molecules are displaced by one chelating nitrate. CCDC：1496645, 1; 1496646, 2.