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The solid-state structures and ligand cavity evaluation of lanthanide(iii) complexes of a DOTA analogue with a (dibenzylamino)methylphosphinate pendant arm.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-01-14 , DOI: 10.1039/c9dt04056k Peter Urbanovský 1 , Jan Kotek , Ivana Císařová , Petr Hermann
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-01-14 , DOI: 10.1039/c9dt04056k Peter Urbanovský 1 , Jan Kotek , Ivana Císařová , Petr Hermann
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A series of lanthanide(iii) complexes of a monophosphinate analogue of H4dota, 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic-10-methyl[(N,N-dibenzylamino)methyl]phosphinic acid (H4do3apDBAm = H4L1), were prepared and their solid-state structures were studied using single-crystal X-ray diffraction. In all structures, the ligand anion was octadentately coordinated to the Ln(iii) or Sc(iii) ions similarly to other DOTA-like ligands, i.e. forming parallel N4- and O4-planes. The lighter lanthanide(iii) complexes (till dysprosium) were nonacoordinated in the twisted square-antiprismatic (TSA) configuration with the apical coordination of water molecules or oxygen atoms from the neighbouring complex unit. The heavier lanthanide(iii) complexes (from terbium) were found as the "anhydrous" octacoordinated twisted square-antiprismatic (TSA') isomer. For the terbium(iii) ion, both forms were structurally characterized. The structural data of the Ln(iii)-H4L1 complexes and complexes of several related DOTA-like ligands were analysed. It clearly showed that the structural parameters for the square-antiprismatic (SA) isomers were clustered in a small range while those for the TSA/TSA' isomers were significantly more spread. The analysis also gave useful information about the influence of various pendant arms on the structure of the complexes of the DOTA-like ligands. The twist angle (torsion) of the chelate ring containing a larger phosphorus atom was similar to those of the remaining three acetate pendants. It led to a larger separation of the N4O4 planes and to smaller trans-O-Ln-O angles than the parameters found in the complexes of H4dota and its tetraamide derivatives dotam(R). It resulted in a relatively long bond between the metal ion and the coordinated water molecule. It led, together with the negative charge of the oxygen atoms forming the O4-plane, to an extremely fast water exchange rate reported for the Gd(iii)-H4L1 complex and, generally, to a fast water exchange of Gd(iii) complexes with the monophosphorus acid analogues of H4dota, H5do3ap/H4do3apR.
中文翻译：
具有（二苄基氨基）甲基次膦酸酯侧链的DOTA类似物的镧系元素（iii）配合物的固态结构和配体腔评估。
H4dota，1,4,7,10-四氮杂环十二烷-1,4,7-三乙酸-10-甲基[（N，N-二苄氨基）甲基]次膦酸（H4do3apDBAm制备），并使用单晶X射线衍射研究其固态结构。在所有结构中，与其他DOTA样配体相似，配体阴离子与Ln（iii）或Sc（iii）离子八齿配位，即形成平行的N4-和O4-平面。较轻的镧系元素（iii）配合物（t）呈扭曲配位形式，并带有邻近配合物单元的水分子或氧原子的顶配位。发现较重的镧系元素（iii）（来自ter）为“无水”八配位扭曲方正棱柱（TSA'）。）异构体。对于the（iii）离子，两种形式均在结构上得到了表征。分析了Ln（iii）-H4L1配合物和几种相关的DOTA样配体的配合物的结构数据。清楚地表明，方形反棱柱（SA）异构体的结构参数聚集在一个较小的范围内，而TSA / TSA'异构体的结构参数分布更广。分析还提供了有关各种侧链对DOTA状配体配合物结构的影响的有用信息。含较大磷原子的螯合环的扭转角（扭转）与其余三个乙酸酯侧基的扭转角（扭转）相似。与H4dota及其四酰胺衍生物dotam（R）的配合物中发现的参数相比，它导致N4O4平面的分离更大，反式O-Ln-O角更小。这导致金属离子和配位的水分子之间的键较长。它与形成O4-平面的氧原子的负电荷一起导致了Gd（iii）-H4L1络合物极快的水交换速率，并且通常导致Gd（iii）络合物的快速水交换。 H4dota的单磷酸类似物H5do3ap / H4do3apR。
更新日期：2020-02-10
中文翻译：
具有（二苄基氨基）甲基次膦酸酯侧链的DOTA类似物的镧系元素（iii）配合物的固态结构和配体腔评估。
H4dota，1,4,7,10-四氮杂环十二烷-1,4,7-三乙酸-10-甲基[（N，N-二苄氨基）甲基]次膦酸（H4do3apDBAm制备），并使用单晶X射线衍射研究其固态结构。在所有结构中，与其他DOTA样配体相似，配体阴离子与Ln（iii）或Sc（iii）离子八齿配位，即形成平行的N4-和O4-平面。较轻的镧系元素（iii）配合物（t）呈扭曲配位形式，并带有邻近配合物单元的水分子或氧原子的顶配位。发现较重的镧系元素（iii）（来自ter）为“无水”八配位扭曲方正棱柱（TSA'）。）异构体。对于the（iii）离子，两种形式均在结构上得到了表征。分析了Ln（iii）-H4L1配合物和几种相关的DOTA样配体的配合物的结构数据。清楚地表明，方形反棱柱（SA）异构体的结构参数聚集在一个较小的范围内，而TSA / TSA'异构体的结构参数分布更广。分析还提供了有关各种侧链对DOTA状配体配合物结构的影响的有用信息。含较大磷原子的螯合环的扭转角（扭转）与其余三个乙酸酯侧基的扭转角（扭转）相似。与H4dota及其四酰胺衍生物dotam（R）的配合物中发现的参数相比，它导致N4O4平面的分离更大，反式O-Ln-O角更小。这导致金属离子和配位的水分子之间的键较长。它与形成O4-平面的氧原子的负电荷一起导致了Gd（iii）-H4L1络合物极快的水交换速率，并且通常导致Gd（iii）络合物的快速水交换。 H4dota的单磷酸类似物H5do3ap / H4do3apR。
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