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Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines.

ABSTRACT: Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)₂(CH₃OH)]?CH₃OH (1) (quin^- = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (pyro), and morpholine (morph). trans-[Cu(quin)₂(pyro)₂] (2) and trans-[Cu(quin)₂(morph)₂] (4) were obtained in good yields. The morpholine system has produced a by-product, trans-[Cu(en)₂(H₂O)₂](morphCOO)₂ (5) (morphCOO^- = morphylcarbamate), a result of the copper(II) quinaldinate reaction with ethylenediamine (en), an inherent impurity in morpholine, and the amine reaction with carbon dioxide. (pyroH)[Cu(quin)₂Cl] (3) forms on the recrystallization of [Cu(quin)₂(pyro)₂] from dichloromethane, confirming a reaction between amine and the solvent. Similarly, a homologous amine, piperidine (pipe), and dichloromethane produced (pipeH)[Cu(quin)₂Cl] (11). The piperidine system has afforded both mono- and bis-amine complexes, [Cu(quin)₂(pipe)] (6) and trans-[Cu(quin)₂(pipe)₂] (7). The latter also exists in solvated forms, [Cu(quin)₂(pipe)₂]?CH₃CN (8) and [Cu(quin)₂(pipe)₂]?CH₃CH₂CN (9). Interestingly, only the piperidine system has experienced a reduction of copper(II). The involvement of amine in the reduction was undoubtedly confirmed by identification of a polycyclic piperidine compound 10, 6,13-di(piperidin-1-yl)dodecahydro-2H,6H-7,14-methanodipyrido[1,2-a:1',2'-e][1,5]diazocine.

SUBMITTER: Modec B

PROVIDER: S-EPMC7180772 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines.

Modec Barbara B Podjed Nina N Lah Nina N

Molecules (Basel, Switzerland) 20200330 7

Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin- = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (py ...[more]

PMID: 32235452

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Project description:The structures of the solvated copper(II) ion in water and nine organic oxygen donor solvents with similar electron-pair donor ability, but with different space-demanding properties at coordination, have been studied by EXAFS. N,N'-Dimethylpropyleneurea and N,N,N',N'-tetramethylurea are sufficiently space demanding at coordination to make the axial positions not accessible, resulting in square-planar copper(II) solvate complexes with an intense green color. The mean Cu-O bond distances in these two solvate complexes are 1.939(3) and 1.935(3) Å, respectively. The best fits of the remaining solvates, which are light blue in different hues, are obtained with a Jahn-Teller distorted-octahedral model consisting of four strongly bound solvent molecules in the equatorial positions at 1.96(2) Å and two in the axial positions but with different Cu-Oax bond distances: ca. 2.15 and 2.32 Å. This is in agreement with observations in solid-state structures of compounds containing hexaaquacopper(II) complexes crystallizing in noncentrosymmetric space groups and all reported crystal structures containing a [Cu(H2O)5(O-ligand)] complex with Jahn-Teller distortion. Such a structure is in agreement with previous EPR and EXAFS studies proving the hydrated copper(II) ion to be a noncentrosymmetric complex in aqueous solution. The refinements of the EXAFS data of the solids [Cu(H2O)6](ClO4)2, [Cu(H2O)6](BrO3)2, [Cu(H2O)6]SiF6, Cu(NO3)2·2.5H2O, and CuSO4·5H2O gave Cu-O bond distances significantly different from those reported in the crystallographic studies but similar to the configuration and bond distances in the hydrated copper(II) ion in aqueous solution. This may depend on whether the orientation of the axial positions is random in one or three dimensions, giving a mean structure of the solid with symmetry higher than that of the individual complexes. This study presents the very first experimental data from the new X-ray absorption spectroscopy beamline Balder at the MAX IV synchrotron radiation facility in Lund, Sweden, as well as the utilized properties of the beamline.

Dataset Information

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines.

Publications

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines.

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