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Article: Spectroscopy, photoredox properties and X-ray crystal structures of triangular gold(I) and silver(I) phosphine complexes

TitleSpectroscopy, photoredox properties and X-ray crystal structures of triangular gold(I) and silver(I) phosphine complexes
Authors
Issue Date1992
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society, Dalton Transactions, 1992 n. 3, p. 427-433 How to Cite?
AbstractThe reaction of HC(PPh2)3 with K[AuCl4] in the presence of 2,2′-thiodiethanol in methanol yielded [Au3{HC(PPh2)3}2Cl]2+. The related [Ag3{HC(PPh2)3}2]3+ was prepared by the reaction of HC(PPh2)3 with Ag(CF3SO3) in dichloromethane. Both complex cations were isolated as perchlorate salts. The X-ray structures of [Au3{HC(PPh2)3}2Cl][ClO 4]2 and [Ag3{HC(PPh2)3}2][ClO 4]3 have been determined: [Au3{HC(PPh2)3}2Cl][ClO 4]2·2MeCN, monoclinic, space group C2/c (no. 15), a = 26.466(3), b = 12.741(2), c = 23.012(5) Å, β = 98.89(1)° and Z = 4; [Ag3{HC(PPh2)3}2][ClO 4]3·2MeCN, monoclinic, space group, P21/n, a = 14.597(4), b = 23.047(2), c = 22.485(3) Å, β = 91.49(2)° and Z = 4. Both [Au3{HC(PPh2)3}2Cl]2+ and [Ag3{HC(PPh2)3}2]3+ consist of three metal atoms arranged in a nearly equilateral triangle with the M-M-M angles close to 60°. The measured intramolecular Ag-Ag and Au-Au distances of 3.1618(5)-3.2228(9) and 2.9220(8)-3.0889(8) Å respectively, indicate that the Au-Au bonding interaction is much stronger than that for Ag-Ag. The UV/VIS spectrum of an acetonitrile solution of [Au3{HC(PPh2)3}2Cl]2+ exhibits intense absorption bands at 270 and 290 nm, assignable to the dσ· → pσ transitions. For [Ag3{HC(PPh2)3}2]3+ the UV/VIS spectrum is virtually identical to that of the free HC(PPh2)3. Excitation of a degassed acetonitrile solution of [Au3{HC(PPh2)3}2Cl]2+ at 300-400 nm at room temperature leads to an observed photoluminescence centred at ca. 537 nm with a lifetime of 11 μs [φ = (1.0 ± 0.1) × 10-3]. The excited-state redox potential, [Au3{HC(PPh2)3}2Cl]3+ + e- → [Au3{HC(PPh2)3}2Cl]2+ *, determined by quenching studies with a series of pyridinium acceptors, is -1.6(2) V vs. saturated sodium chloride calomel electrode (SSCE).
Persistent Identifierhttp://hdl.handle.net/10722/168192
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorYip, HKen_US
dc.contributor.authorYam, VWWen_US
dc.contributor.authorCheung, PYen_US
dc.contributor.authorLai, TFen_US
dc.contributor.authorShieh, SJen_US
dc.contributor.authorPeng, SMen_US
dc.date.accessioned2012-10-08T03:16:07Z-
dc.date.available2012-10-08T03:16:07Z-
dc.date.issued1992en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1992 n. 3, p. 427-433en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168192-
dc.description.abstractThe reaction of HC(PPh2)3 with K[AuCl4] in the presence of 2,2′-thiodiethanol in methanol yielded [Au3{HC(PPh2)3}2Cl]2+. The related [Ag3{HC(PPh2)3}2]3+ was prepared by the reaction of HC(PPh2)3 with Ag(CF3SO3) in dichloromethane. Both complex cations were isolated as perchlorate salts. The X-ray structures of [Au3{HC(PPh2)3}2Cl][ClO 4]2 and [Ag3{HC(PPh2)3}2][ClO 4]3 have been determined: [Au3{HC(PPh2)3}2Cl][ClO 4]2·2MeCN, monoclinic, space group C2/c (no. 15), a = 26.466(3), b = 12.741(2), c = 23.012(5) Å, β = 98.89(1)° and Z = 4; [Ag3{HC(PPh2)3}2][ClO 4]3·2MeCN, monoclinic, space group, P21/n, a = 14.597(4), b = 23.047(2), c = 22.485(3) Å, β = 91.49(2)° and Z = 4. Both [Au3{HC(PPh2)3}2Cl]2+ and [Ag3{HC(PPh2)3}2]3+ consist of three metal atoms arranged in a nearly equilateral triangle with the M-M-M angles close to 60°. The measured intramolecular Ag-Ag and Au-Au distances of 3.1618(5)-3.2228(9) and 2.9220(8)-3.0889(8) Å respectively, indicate that the Au-Au bonding interaction is much stronger than that for Ag-Ag. The UV/VIS spectrum of an acetonitrile solution of [Au3{HC(PPh2)3}2Cl]2+ exhibits intense absorption bands at 270 and 290 nm, assignable to the dσ· → pσ transitions. For [Ag3{HC(PPh2)3}2]3+ the UV/VIS spectrum is virtually identical to that of the free HC(PPh2)3. Excitation of a degassed acetonitrile solution of [Au3{HC(PPh2)3}2Cl]2+ at 300-400 nm at room temperature leads to an observed photoluminescence centred at ca. 537 nm with a lifetime of 11 μs [φ = (1.0 ± 0.1) × 10-3]. The excited-state redox potential, [Au3{HC(PPh2)3}2Cl]3+ + e- → [Au3{HC(PPh2)3}2Cl]2+ *, determined by quenching studies with a series of pyridinium acceptors, is -1.6(2) V vs. saturated sodium chloride calomel electrode (SSCE).en_US
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_US
dc.relation.ispartofJournal of the Chemical Society, Dalton Transactionsen_US
dc.titleSpectroscopy, photoredox properties and X-ray crystal structures of triangular gold(I) and silver(I) phosphine complexesen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.emailYam, VWW:wwyam@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.identifier.authorityYam, VWW=rp00822en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1039/DT9920000427en_US
dc.identifier.scopuseid_2-s2.0-37049073260en_US
dc.identifier.issue3en_US
dc.identifier.spage427en_US
dc.identifier.epage433en_US
dc.identifier.isiWOS:A1992HD31900013-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridYip, HK=15068942100en_US
dc.identifier.scopusauthoridYam, VWW=18539304700en_US
dc.identifier.scopusauthoridCheung, PY=23066385600en_US
dc.identifier.scopusauthoridLai, TF=7202203523en_US
dc.identifier.scopusauthoridShieh, SJ=7102172797en_US
dc.identifier.scopusauthoridPeng, SM=35464852200en_US

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