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Novel primary amide-based cationic metal complexes: green synthesis, crystal structures, Hirshfeld surface analysis and solvent-free cyanosilylation reaction

Abstract

A new symmetrical and flexible primary amide functionalized ligand, 2,2'-(ethane-1,2-diylbis((pyridin-2-ylmethyl)azanediyl))diacetamide (2-BPEG), has been synthesized and structurally characterized. Using this multidenate ligand, four novel metal complexes, namely [Cu(2-BPEG)](ClO4)2.0.5H2O (1), [Zn(2-BPEG)](ClO4)2 (2), [Zn(2-BPEG)](ZnCl4).H2O (3) and [Cd(2-BPEG)(H2O)](ClO4)2.H2O (4), have been synthesized under ambient conditions and characterized by elemental, spectroscopic and thermal analysis, and single and powder X-ray diffraction. Complexes 1-3 are hexacoordinated with an N4O2 donor set (provided by the hexadentate 2-BPEG ligand) while Complex 4 is heptacoordinated with an additional coordinated water molecule. In all cases, the 2-BPEG ligand acts as a hexadentae ligand. A change in the starting metal salt has resulted in the formation of 2 and 3 with different tetrahedral anions, ClO4- and ZnCl4-, respectively. This has provided an opportunity to showcase anion-directed supramolcular networks for these compounds. Compounds 1, 2 and 4 with perchlorate anions show similar and comparable intermolecular interactions in their 3D networks. On the other hand, the supramolecular self-assembly of 3 is dominated by a variety of intermolecular interactions such as C–H⋯Cl, N–H⋯Cl, O–H⋯Cl and C–H⋯O due to the presence of tetrachlorozincate(II) ion. Moreover, the role of weak intermolecular interactions in the crystal packing has been analysed and quantified using Hirshfeld surface analysis. Furthermore, compound 4 exhibiting open Lewis acid site has been found to be a very efficient and recyclable heterogeneous catalyst for the solvent-free cyanosilylation of various aldehydes with trimethylsilyl cyanide (TMSCN) producing the corresponding trimethylsilyl ether in high yields.

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Publication details

The article was received on 03 Dec 2018, accepted on 12 Feb 2019 and first published on 12 Feb 2019


Article type: Paper
DOI: 10.1039/C8DT04773A
Citation: Dalton Trans., 2019, Accepted Manuscript

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    Novel primary amide-based cationic metal complexes: green synthesis, crystal structures, Hirshfeld surface analysis and solvent-free cyanosilylation reaction

    D. Markad, S. Khullar and S. Mandal, Dalton Trans., 2019, Accepted Manuscript , DOI: 10.1039/C8DT04773A

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