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Issue 5, 2014
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How to force a classical chelating ligand to a metal non-chelating bridge: the observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n

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Abstract

The novel chain coordination polymer {[Cu2(Piv)4(H3tBuDea)](Piv)}n (1) has been prepared through the self-assembly reaction of copper(II) nitrate with pivalic acid (HPiv) and N-tert-butyldiethanolamine (H2tBuDea) in acetonitrile solution. Crystallographic analysis revealed the extremely rare non-chelating bridging coordination mode of diethanolamine ligand in 1, observed for the first time in transition metal complexes, as well as in complexes of diethanolamine having a non-coordinating aliphatic group at the N atom. Possible reasons for such a coordination and analysis of the main coordination modes of diethanolamine-based ligands are discussed. Variable-temperature (1.8–300 K) magnetic susceptibility measurements showed that 1 represents a rare example of dicopper(II) tetracarboxylate that is a diamagnetic solid at room temperature. This behaviour is compared with literature examples and discussed on the basis of DFT calculations. Furthermore, 1 acts as an efficient catalyst for the mild hydrocarboxylation of linear and cyclic C5–C8 alkanes into the corresponding carboxylic acids.

Graphical abstract: How to force a classical chelating ligand to a metal non-chelating bridge: the observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n

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Publication details

The article was received on 20 Aug 2013, accepted on 05 Oct 2013 and first published on 13 Nov 2013


Article type: Paper
DOI: 10.1039/C3CE41657G
Citation: CrystEngComm, 2014,16, 775-783
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    How to force a classical chelating ligand to a metal non-chelating bridge: the observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n

    O. V. Nesterova, M. V. Kirillova, M. F. C. Guedes da Silva, R. Boča and A. J. L. Pombeiro, CrystEngComm, 2014, 16, 775
    DOI: 10.1039/C3CE41657G

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