Publication | Closed Access
Titanium(<scp>iv</scp>)-based helicates incorporating the ortho-phenylenediamine ligand: a structural and a computational investigation
10
Citations
55
References
2017
Year
The multicomponent coordination chemistry involving Ti(OPr<sup>i</sup>)<sub>4</sub>, the ortho-phenylenediamine ligand (opda) and 2,2'-biphenol-based proligands (L<sup>2</sup>H<sub>4</sub> and L<sup>3</sup>H<sub>6</sub>) is described. The proligands L<sup>2</sup>H<sub>4</sub> and L<sup>3</sup>H<sub>6</sub> incorporate two and three 2,2'-biphenol units linked with p-phenylene bridges (p-PLB) respectively. We demonstrate that this selected set of components allows the spontaneous formation of neutral double-stranded helicates. In particular, we report the X-ray crystal structure of a multicomponent helicate formed with L<sub>2</sub>, named Ti<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>(opda)<sub>2</sub>. The molecular structure of the helicate shows two inequivalent L<sup>2</sup> ligands. <sup>1</sup>H NMR analysis at variable temperature highlights an intramolecular fluxional phenomenon for this species. An insight into this dynamic behaviour is obtained via the energy profiles of Ti<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>(opda)<sub>2</sub> resulting from the full rotation of the p-PLB rings. Additionally, the thermodynamic parameters associated with the formation of the Ti<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>(opda)<sub>2</sub> complex are modelled and discussed related to the ones linked to the formation of a related monomeric complex.
| Year | Citations | |
|---|---|---|
Page 1
Page 1