From Gas Phase Observations to Solid State Reality: The Identification and Isolation of Trinuclear Salicylaldoximato Copper Complexes

dc.citation.issue19
dc.citation.volume27
dc.contributor.authorRoach BD
dc.contributor.authorForgan RS
dc.contributor.authorKamenetzky E
dc.contributor.authorParsons S
dc.contributor.authorPlieger PG
dc.contributor.authorWhite FJ
dc.contributor.authorWoodhouse S
dc.contributor.authorTasker PA
dc.contributor.editorMorazzoni F
dc.coverage.spatialSwitzerland
dc.date.accessioned2024-01-10T00:40:27Z
dc.date.accessioned2024-07-25T06:45:25Z
dc.date.available2022-09-29
dc.date.available2024-01-10T00:40:27Z
dc.date.available2024-07-25T06:45:25Z
dc.date.issued2022-09-29
dc.description.abstractConditions have been identified in which phenolic aldoximes and ketoximes of the types used in commercial solvent extraction processes can be doubly deprotonated and generate polynuclear Cu complexes with lower extractant:Cu molar ratios than those found in commercial operations. Electrospray mass spectrometry has provided an insight into the solution speciation in extraction experiments and has identified conditions to allow isolation and characterization of polynuclear Cu-complexes. Elevation of pH is effective in enhancing the formation of trinuclear complexes containing planar {Cu3-μ3-O}4+ or {Cu3-μ3-OH}5+ units. DFT calculations suggest that such trinuclear complexes are more stable than other polynuclear species. Solid structures of complexes formed by a salicylaldoxime with a piperidino substituent ortho to the phenolic OH group (L9H2) contain two trinuclear units in a supramolecular assembly, {[Cu3OH(L9H)3(ClO4)](ClO4)} 2, formed by H-bonding between the central {Cu3-μ3-OH}5+ units and oxygen atoms in the ligands of an adjacent complex. Whilst the lower ligand:Cu molar ratios provide more efficient Cu-loading in solvent extraction processes, the requirement to raise the pH of the aqueous phase to achieve this will make it impractical in most commercial operations because extraction will be accompanied by the precipitation (as oxyhydroxides) of Fe(III) which is present in significant quantities in feed solutions generated by acid leaching of most Cu ores.
dc.description.confidentialfalse
dc.edition.editionOctober 2022
dc.format.pagination6421-
dc.identifier.author-urlhttps://www.ncbi.nlm.nih.gov/pubmed/36234958
dc.identifier.citationRoach BD, Forgan RS, Kamenetzky E, Parsons S, Plieger PG, White FJ, Woodhouse S, Tasker PA. (2022). From Gas Phase Observations to Solid State Reality: The Identification and Isolation of Trinuclear Salicylaldoximato Copper Complexes.. Molecules. 27. 19. (pp. 6421-).
dc.identifier.doi10.3390/molecules27196421
dc.identifier.eissn1420-3049
dc.identifier.elements-typejournal-article
dc.identifier.issn1420-3049
dc.identifier.number6421
dc.identifier.piimolecules27196421
dc.identifier.urihttps://mro.massey.ac.nz/handle/10179/70802
dc.languageeng
dc.publisherMDPI (Basel, Switzerland)
dc.publisher.urihttps://www.mdpi.com/1420-3049/27/19/6421
dc.relation.isPartOfMolecules
dc.subjectCu extraction
dc.subjectElectrospray mass spectrometry
dc.subjectoxime proligands
dc.subjectsolvent extraction
dc.subjecttrinuclear complexes
dc.subjectCopper
dc.subjectFerric Compounds
dc.subjectLigands
dc.subjectOximes
dc.subjectOxygen
dc.subjectSolvents
dc.titleFrom Gas Phase Observations to Solid State Reality: The Identification and Isolation of Trinuclear Salicylaldoximato Copper Complexes
dc.typeJournal article
pubs.elements-id457363
pubs.organisational-groupOther
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