4 research outputs found
Ditopic Extractants to Separate Palladium(II) and Platinum(IV) Chloridometalates via Inner or Outer Sphere Binding
Anion receptor design; exploiting outer sphere coordination chemistry to obtain high selectivity for chloridometalates over chloride.
High
anion selectivity for PtCl<sub>6</sub><sup>2–</sup> over Cl<sup>–</sup> is shown by a series of amidoamines, R<sup>1</sup>R<sup>2</sup>NCOCH<sub>2</sub>CH<sub>2</sub>NR<sup>3</sup>R<sup>4</sup> (L1 with R<sup>1</sup> = R<sup>4</sup> = benzyl and R<sup>2</sup> = R<sup>3</sup> = phenyl and L3 with R<sup>1</sup> = H, R<sup>2</sup> = 2-ethylhexyl, R<sup>3</sup> = phenyl and R<sup>4</sup> = methyl),
and amidoethers, R<sup>1</sup>R<sup>2</sup>NCOCH<sub>2</sub>CH<sub>2</sub>OR<sup>3</sup> (L5 with R<sup>1</sup> = H, R<sup>2</sup> =
2-ethylhexyl and R<sup>3</sup> = phenyl), which provide receptor sites
which extract PtCl<sub>6</sub><sup>2–</sup> preferentially
over Cl<sup>–</sup> in extractions from 6 M HCl solutions.
The amidoether receptor L5 was found to be a much weaker extractant
for PtCl<sub>6</sub><sup>2–</sup> than its amidoamine analogues.
Density functional theory calculations indicate that this is due to
the difficulty in protonating the amidoether to generate a cationic
receptor, LH<sup>+</sup>, rather than the latter showing weaker binding
to PtCl<sub>6</sub><sup>2–</sup>. The most stable forms of
the receptors, LH<sup>+</sup>, contain a tautomer in which the added
proton forms an intramolecular hydrogen bond to the amide oxygen atom
to give a six-membered proton chelate. Dispersion-corrected DFT calculations
appear to suggest a switch in ligand conformation for the amidoamine
ligands to an open tautomer state in the complex, such that the cationic
N–H or O–H groups are also readily available to form
hydrogen bonds to the PtCl<sub>6</sub><sup>2–</sup> ion, in
addition to the array of polarized C–H bonds. The predicted
difference in energies between the proton chelate and nonchelated
tautomer states for L1 is small, however, and the former is found
in the X-ray crystal structure of the assembly [(L1H)<sub>2</sub>PtCl<sub>6</sub>]. The DFT calculations and the X-ray structure indicate that
all LH<sup>+</sup> receptors present an array of polarized C–H
groups to the large, charge diffuse PtCl<sub>6</sub><sup>2–</sup> anion resulting in high selectivity of extraction of PtCl<sub>6</sub><sup>2–</sup> over the large excess of chloride
On the Extraction of HCl and H<sub>2</sub>PtCl<sub>6</sub> by Tributyl Phosphate: A Mode of Action Study
<p>Combining computational modeling with experimental measurements has revealed the self-assembly of nano-aggregate structures in the transfer of HCl and PtCl<sub>6</sub><sup>2–</sup> from an aqueous phase into toluene by the common industrial extractant tributyl phosphate (TBP). Molecular dynamics simulations have been coupled to analytical measurements to provide an atomistic interpretation of the mode of action of TBP under 6 M and 10 M HCl conditions. The structures conform to reverse micelles, where the Cl<sup>–</sup> or PtCl<sub>6</sub><sup>2–</sup> core is encapsulated by a hydration shell that acts as a mediating bridge to the electronegative oxygen atom in the TBP phosphate groups. For the 6 M HCl extraction model, the data support stable aggregates forming from 2–3 TBP molecules around one chloride anion if the number of water molecules encapsulating the chloride anion is no more than five; increasing the water content to 10 molecules allows a fourth TBP molecule to coordinate. For the 10 M HCl extraction model, stable structures are obtained that conform to the empirical formula (TBP.HCl.H<sub>2</sub>O)<sub>3–5</sub>. At 6 M HCl, extraction of PtCl<sub>6</sub><sup>2–</sup> is achieved by encapsulation by four TBP molecules; the data for extraction at 10 M HCl indicate larger aggregates containing multiple PtCl<sub>6</sub><sup>2–</sup> anions are likely to be forming. In all cases, the hydrated core regions of the reverse micelles are considerably exposed. The diameters of the self-assembled structures around chloride ions agree well with available literature data from small-angle neutron-scattering experiments.</p