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Article: Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

TitleSynthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species
Authors
KeywordsAb initio modelling
Analogous reactions
Charge state
Diphosphine ligand
Experimental data
Issue Date2012
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Dalton Transactions, 2012, v. 41 n. 16, p. 4789-4798 How to Cite?
AbstractA mixture of cyclic gold(I) complexes [Au(2)(mu-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(mu-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(mu-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(mu-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.
Persistent Identifierhttp://hdl.handle.net/10722/159359
ISSN
2023 Impact Factor: 3.5
2023 SCImago Journal Rankings: 0.697
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorBhargava, Sen_US
dc.contributor.authorKitadai, Ken_US
dc.contributor.authorMasashi, Ten_US
dc.contributor.authorDrumm, DWen_US
dc.contributor.authorRusso, SPen_US
dc.contributor.authorYam, VWWen_US
dc.contributor.authorLee, TKMen_US
dc.contributor.authorWagler, Jen_US
dc.contributor.authorMirzadeh, Nen_US
dc.date.accessioned2012-08-16T05:48:51Z-
dc.date.available2012-08-16T05:48:51Z-
dc.date.issued2012en_US
dc.identifier.citationDalton Transactions, 2012, v. 41 n. 16, p. 4789-4798en_US
dc.identifier.issn1477-9226-
dc.identifier.urihttp://hdl.handle.net/10722/159359-
dc.description.abstractA mixture of cyclic gold(I) complexes [Au(2)(mu-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(mu-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(mu-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(mu-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.-
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_US
dc.relation.ispartofDalton Transactionsen_US
dc.subjectAb initio modelling-
dc.subjectAnalogous reactions-
dc.subjectCharge state-
dc.subjectDiphosphine ligand-
dc.subjectExperimental data-
dc.titleSynthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity speciesen_US
dc.typeArticleen_US
dc.identifier.emailBhargava, S: Suresh.bhargava@rmit.edu.auen_US
dc.identifier.emailYam, VWW: wwyam@hku.hk-
dc.identifier.authorityYam, VWW=rp00822en_US
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/c2dt11722c-
dc.identifier.pmid22382206-
dc.identifier.scopuseid_2-s2.0-84859243914-
dc.identifier.hkuros204730en_US
dc.identifier.volume41en_US
dc.identifier.issue16-
dc.identifier.spage4789en_US
dc.identifier.epage4798en_US
dc.identifier.isiWOS:000302023800012-
dc.publisher.placeUnited Kingdom-
dc.identifier.issnl1477-9226-

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