Synthesis of New Binucleating Cylindrical Macrotricyclic Ligands Where Two Cyclam Rings Are in a Face-to-Face Conformation. Characterization of Their Dicopper(II) and Dinickel(II) Complexes
Synthesis of New Binucleating Cylindrical Macrotricyclic Ligands Where Two Cyclam Rings Are in a Face-to-Face Conformation. Characterization of Their Dicopper(II) and Dinickel(II) Complexes
复制标题
两个仙客来环面对面构象的新型双核圆柱大三环配体的合成。
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
R. Weiss
中科院分区：
文献类型：
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作者：
M. Lachkar;R. Guilard;A. Atmani;A. Cian;A. Fischer;R. Weiss
合成了新的对称圆柱形大三环配体1a，b，其中两个环基亚基通过两个不同长度的芳香链（间二甲苯基，对二甲苯基）通过氮原子连接。这些化合物是根据五步程序制备的。易得的三杂环环4与相应的双（溴乙基）苯反应生成双环环中间体5a，b。叔丁基氧羰基选择性脱保护生成二胺双大环6a，b。这些二胺与适当的二氯二酸在高稀释条件下缩合得到二胺大三环7a，b，收率很高。还原酰胺基团和去保护甲酰基后，得到新的圆柱形大三环1a、b。大三环配体1a，b配位Cu2+和Ni2+形成双核物质。用单晶法测定了[Ni2(1a)](ClO4)4·2CH3CN配合物的晶体结构。
Synthesis of new symmetrical cylindrical macrotricyclic ligands 1a,b, where two cyclam subunits are linked through nitrogen atoms by two aromatic chains of various lengths (meta-xylylenyl, para-xylylenyl) has been achieved. These compounds have been prepared according a five step procedure. The readily available trisheteroprotected cyclam 4 has been reacted with the appropriate bis(bromomethyl)benzene to give the bimacrocycle intermediates 5a,b. The selective deprotection of the tert-butyloxycarbonyl group leads to the diamine bimacrocycles 6a,b. Condensation of these diamines with the appropriate diacid dichloride under high-dilution conditions yields the diamide macrotricycles 7a,b in a significant yield. After reduction of the amide moieties and deprotection of the tosyl groups, new cylindrical macrotricycles 1a,b were obtained. Macrotricyclic ligands 1a,b coordinate Cu2+ and Ni2+ to form binuclear species. The crystal structure of the [Ni2(1a)](ClO4)4·2CH3CN complex has been determined by single-cryst...