L.V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Science of Ukraine, Prospekt Nauki 31, 03028, Kiev-28, Ukraine.
Dalton Trans. 2010 Sep 7;39(33):7706-13. doi: 10.1039/c0dt00376j. Epub 2010 Jul 23.
The crystal structures of the palladium(II) complexes of the open-chain and macrocyclic ligands PdL(1).3H(2)O, PdL(2).6H(2)O and PdL(3).5H(2)O have been determined (H(2)L(1) = 1,4,8,11-tetraazaundecane-5,7-dione, H(2)L(2) = 1,4,8,11-tetraazacyclotetradecane-5,7-dione, H(2)L(3) = 1,4,8,11-tetraazacyclotridecane-5,7-dione). The coordination polyhedra of the palladium(II) ions in all complexes are formed by two deprotonated amide and two amine donors with Pd-N distances being similar in PdL(1) and PdL(2) and substantially shorter in PdL(3). A detailed analysis of the (1)H NMR spectra of the macrocyclic complexes supports the formation in aqueous solution of only N-meso isomers of both compounds in agreement with the X-ray data. The spectra of the palladium(II) macrocyclic complexes are shifted downfield as a whole as compared to those of the nickel(II) analogues with the shifts being essentially non-uniform. The latter feature can be related to the differences in magnetic anisotropy of the M-N bonds. The maxima of d-d absorption bands of the palladium(II) complexes demonstrate weaker dependence on the macrocycle size as compared to those of the nickel(II) analogues. Both macrocyclic compounds PdL(2).6H(2)O and PdL(3).5H(2)O are characterized by lamellar crystal structures consisting of interleaved layers formed by macrocyclic units and by water molecules with similar metal complex layers and different 2D water sheets. A columnar crystal structure is inherent for PdL(1).3H(2)O with the water molecules present as discrete (H(2)O)(3) clusters.
钯（II）配合物的晶体结构
开放链和大环配体 PdL(1).3H(2)O、PdL(2).6H(2)O 和 PdL(3).5H(2)O 的钯（II）配合物的晶体结构已经确定（H(2)L(1) = 1,4,8,11-四氮杂十一烷-5,7-二酮，H(2)L(2) = 1,4,8,11-四氮杂环十四烷-5,7-二酮，H(2)L(3) = 1,4,8,11-四氮杂环十三烷-5,7-二酮）。所有配合物中钯（II）离子的配位多面体由两个去质子酰胺和两个胺供体形成，Pd-N 距离在 PdL(1) 和 PdL(2) 中相似，在 PdL(3) 中明显缩短。对大环配合物的（1）H NMR 谱的详细分析支持在水溶液中仅形成两种化合物的 N-中位异构体，这与 X 射线数据一致。与镍（II）类似物相比，钯（II）大环配合物的光谱整体向高场移动，且移动基本上不均匀。后一个特征可以与 M-N 键的磁各向异性差异有关。钯（II）配合物的 d-d 吸收带的最大值与镍（II）类似物相比，对大环尺寸的依赖性较弱。与镍（II）类似物相比，两种大环化合物 PdL(2).6H(2)O 和 PdL(3).5H(2)O 的特征均为层状晶体结构，由大环单元和水分子形成的层状结构组成，具有相似的金属配合物层和不同的二维水层。PdL(1).3H(2)O 具有柱状晶体结构，其中水分子以离散的（H(2)O）(3)簇的形式存在。
