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 {[Cu-2(Piv)(4)(H(3)tBuDea)](Piv)}(n)

Nesterova, OV; Kirillova, MV; Guedes da Silva, MFC; Boca, R; Pombeiro, AJL

HERO ID

4660932

Reference Type

Journal Article

Year

2014

HERO ID 4660932
In Press No
Year 2014
Title 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 {[Cu-2(Piv)(4)(H(3)tBuDea)](Piv)}(n)
Authors Nesterova, OV; Kirillova, MV; Guedes da Silva, MFC; Boca, R; Pombeiro, AJL
Journal CrystEngComm
Volume 16
Issue 5
Page Numbers 775-783
Abstract The novel chain coordination polymer {[Cu-2(Piv)(4)(H(3)tBuDea)](Piv)}(n) (1) has been prepared through the self-assembly reaction of copper(II) nitrate with pivalic acid (HPiv) and N-tert-butyldiethanolamine (H(2)tBuDea) 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 C-5-C-8 alkanes into the corresponding carboxylic acids.
Doi 10.1039/c3ce41657g
Wosid WOS:000328952000006
Is Certified Translation No
Dupe Override No
Is Public Yes