Molecular Structures of Dipeptide-Palladium (II) Conjugated Complexes
Molecular Structures of Dipeptide-Palladium (II) Conjugated Complexes
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二肽-钯 (II) 共轭配合物的分子结构
DOI：
10.1002/ejic.201400131
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发表时间：
2014
影响因子：
2.3
通讯作者：
Yuki Sakamoto
中科院分区：
文献类型：
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作者：
Yuki Sakamoto;Toshiyuki Moriuchi;and Toshikazu Hirao;Yuki Sakamoto
NCN钳形钯（II）配合物作为有机金属化合物和尿嘧啶衍生物作为核碱基的组合，设计了含有6 -乙基- 1 -辛基脲嘧啶片段的NCN钳形钯（II）配合物，以获得生物有机金属化合物。NCN钳形配体与Pd(dba)2（dba =二苄基丙酮）反应生成了NCN钳形钯（II）配合物expd‐Br。用AgOTf （OTf =三氟甲磺酸盐）在乙腈中处理pd - br制备的阳离子配合物expd - MeCN的晶体结构表明，两个独立分子的尿嘧啶部分之间通过分子间氢键形成二聚体结构。发现NCN钳形钯（II）配合物的自组装性能依赖于辅助配体。每个氢键二聚体通过一个分子间的氢键桥连接在配位水分子和阳离子配合物中的三酸阴离子之间。在NCN钳形钯（II）配合物expd‐OTf中观察到尿嘧啶部分和与钯中心结合的三酸阴离子之间的分子间氢键，尽管在NCN钳形钯（II）配合物expd‐O2CCF3中尿嘧啶部分之间形成了二聚体结构，这是通过从mpd‐Brwith AgO2CCF3中提取溴离子得到的。
NCN pincer palladium(II) complexes bearing a 6‐ethynyl‐1‐octyluracil moiety were designed by the combination of an NCN pincer palladium(II) complexes as an organometallic compound and a uracil derivative as a nucleobase to afford bioorganometallic compounds. The reaction of the NCN pincer ligand with Pd(dba)2(dba = dibenzylideneacetone) led to the formation of the NCN pincer palladium(II) complexPd‐Br. The crystal structure of the cationic complexPd‐MeCN, which was prepared by the treatment ofPd‐Brwith AgOTf (OTf = trifluoromethanesulfonate) in acetonitrile, revealed that a dimeric structure formed through intermolecular hydrogen bonds between the uracil moieties of two independent molecules. The self‐assembly properties of the NCN pincer palladium(II) complexes were found to depend on the ancillary ligands. Each hydrogen‐bonded dimer was connected through an intermolecular hydrogen‐bonding bridge between the coordinated water molecule and the triflate anion in the cationic complexPd‐H2O. Intermolecular hydrogen bonding between the uracil moiety and the triflate anion bound to the palladium center was observed in the NCN pincer palladium(II) complexPd‐OTf, although a dimeric structure between the uracil moieties was formed in the NCN pincer palladium(II) complexPd‐O2CCF3, which was obtained by the abstraction of the bromide ion fromPd‐Brwith AgO2CCF3.