Chemical Science Division, Glenn T. Seaborg Center, Lawrence Berkeley National Laboratory (LBNL), Berkeley, California 94720, USA.
Inorg Chem. 2009 Dec 21;48(24):11489-91. doi: 10.1021/ic901815b.
Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO(2))(2)L(2) species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substitutents and linking amides.
单核铀酰配合物的结构表征与四齿、噻吩连接的双（3-羟基-N-甲基-2-吡啶酮）配体，揭示了此类配体的最平面配位几何结构。噻吩连接链上引入乙硫基基团破坏了这种平面共轭配体排列，导致二聚体（UO 2 ） 2 L 2 物种的形成，其中每个配体跨越两个铀酰中心。相对能量计算表明，这种二聚体形成的趋势是乙基硫取代基和连接酰胺之间的空间位阻干扰的结果。
