Self-Assembly of Coordination Polymers from Volatile PdII and PbII β-Diketonate Derivatives through Metallophilic Interactions
Self-Assembly of Coordination Polymers from Volatile PdII and PbII β-Diketonate Derivatives through Metallophilic Interactions
复制标题
挥发性 PdII 和 PbII β-二酮衍生物通过亲金属相互作用自组装配位聚合物
DOI：
10.1002/ejic.201300876
复制
发表时间：
2013
影响因子：
2.3
通讯作者：
I. Igumenov
中科院分区：
文献类型：
--
作者：
V. Krisyuk;I. Baidina;T. Basova;L. G. Bulusheva;I. Igumenov
基于中性金属β-二酮衍生物的新型双金属配位聚合物可以在有机溶剂中通过简单的共结晶得到。用X-射线单晶衍射法研究了双金属配合物[反式Pd(KI)2]*[Pb(HFA)2](1；KI=2-亚氨基戊烷-4-酮酸酯，HFA=1，1，1，5，5，5-六氟戊烷-2，4-二酸酯)，[cis-Pd(KI)2]*[铅(HFA)2](2)和[反式Pd(Tmha)2]*[Pb(HFA)2]2(3；tmha=2，2，6，6-四甲基-3-亚氨基庚烷-5-酮酸酯)。1和3的晶体由含有交替的金属络合物分子的配位聚合物链组成。2的晶体是由四金属物种组成的。定向的非共价金属-金属相互作用与桥联配体原子结合在这些异金属配位化合物的配位聚合物上。报道了在一系列类似化合物中形成PdII···PbII亲金属相互作用的结构证据。通过比较计算和实验的红外光谱，可以确定100-600厘米-1区域内的吸收带，这些吸收带对应于由这种相互作用产生的金属原子的合作振动。这些新型配位聚合物的构型可以利用配位配体的空间和电子因素来设计。
New dimetallic coordination polymers based on neutral metal β-diketonate derivatives can be obtained by simple cocrystallization from organic solvents. X-ray crystallography studies have been performed for the dimetallic complexes [trans-Pd(ki)2]*[Pb(hfa)2] (1; ki = 2-iminopentan-4-onate, hfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate), [cis-Pd(ki)2]*[Pb(hfa)2] (2), and [trans-Pd(tmha)2]*[Pb(hfa)2]2 (3; tmha = 2,2,6,6-tetramethyl-3-iminoheptan-5-onate). The crystals of 1 and 3 are composed of chains of coordination polymers containing alternating molecules of the metal complexes. The crystals of 2 are composed of tetrametallic species. Directed noncovalent metal–metal interactions along with the bridging ligand atoms bind the coordination polymers of these heterometallic coordination compounds. Structural evidence is reported for the formation of PdII···PbII metallophilic interactions in a series of similar compounds. A comparison of the calculated and experimental IR spectra allowed determination of the absorption bands in the region 100–600 cm–1 that correspond to the cooperative vibrations of the metal atoms that result from such interactions. The steric and electronic factors of the chelate ligands can be used to design the architecture of these new coordination polymers.