Unsolvated homo- and heterometallic highly fluorinated β-diketonate complexes of copper(II)
Unsolvated homo- and heterometallic highly fluorinated β-diketonate complexes of copper(II)
复制标题
DOI：
10.1016/j.poly.2018.09.048
复制
发表时间：
2019-01-01
期刊：
影响因子：
2.6
通讯作者：
Petrukhina, Marina A.
中科院分区：
文献类型：
--
作者：
Crowder, Janell M.;Han, Haixiang;Petrukhina, Marina A.
(T)he制备具有双（五氟苯甲酰基）甲烷配体（L，C6 F5 COCHCOC 6 F5-）的非溶剂化Cu（II）络合物，并使用气相升华-沉积在150 ℃下结晶为[CuL 2]（1）。X射线晶体学表征证实了1的中心对称单核结构，其具有围绕Cu（II）的正方形平面几何形状（Cu-O-av 1.9149（8）埃）。1与六氟乙酰丙酮钠[Na（hfac）]在无溶剂条件下反应，得到第一个异金属钠铜β-二酮化合物[Na 2Cu 2L 4（hfac）（2）]（2），其结构经单晶X射线衍射表征。在2的中心对称四核结构中，二聚体[Na（hfac）]（2）单元夹在两个CuL 2单元之间。L-配体通过它们的一个O-原子在Cu和Na之间起螯合-桥接作用。hfac配体通过两个O原子在Cu和Na之间以及Na（1）和Na（1A）之间进行螯合-桥接。除了五个主要的Na-O相互作用（av. 2.4109（17）埃），三个次级Na-F接触（平均值。2.6006（15）埃）的贡献，为钠的整体扭曲的正方形反棱柱配位环境。Cu的几何形状为四方锥形，Cu-O（L）距离平均为1.922（14）埃，Cu-O（hfac）为2.3021（15）埃。当在环境压力下在氩气中在230 ° C下进行时，2的热分解产生NaCuF 3、Na 2CuF 4和NaF的混合物。(C)2018爱思唯尔有限公司版权所有
(T)he unsolvated Cu(II) complex with bis(pentafluorobenzoyl)methanide ligand (L, C6F5COCHCOC6F5-) is prepared and crystallized as [CuL2] (1) using gas phase sublimation-deposition at 150 degrees C. The X-ray crystallographic characterization confirmed the centrosymmetric mononuclear structure of 1 with a square planar geometry around Cu(II) (Cu-O-av 1.9149(8) angstrom). The reaction of 1 with sodium hexafluoroacetylacetonate [Na(hfac)] in a solvent-free environment afforded [Na2Cu2L4(hfac)(2)](2), the first heterometallic Na-Cu beta-diketonate characterized by single-crystal X-ray diffraction. In the centrosymmetric tetranuclear structure of 2, a dimeric [Na(hfac)](2) unit is sandwiched between two CuL2 units. The L-ligands function as chelating-bridging between Cu and Na through one of their O-atoms. The hfac ligands are chelating-bridging between Cu and Na and between Na(1) and Na(1A) through both O-atoms. In addition to the five primary Na-O interactions (av. 2.4109(17) angstrom), three secondary Na-F contacts (av. 2.6006 (15) angstrom) contribute to the overall distorted square antiprismatic coordination environment for Na. The geometry of Cu is square pyramidal with Cu-O(L) distances averaging at 1.922(14) angstrom and Cu-O(hfac) of 2.3021(15) angstrom. Thermal decomposition of 2 yields a mixture of NaCuF3, Na2CuF4 and NaF, when conducted at 230 degrees C in argon at ambient pressure. (C) 2018 Elsevier Ltd. All rights reserved.