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Article: Syntheses, electrochemistry, photophysics and photochemistry of nitridorhenium(v) diphosphine complexes and related nitridorhenium(v) organometallics; crystal structure of [RevN(C≡CBut)2(PPh3) 2]

TitleSyntheses, electrochemistry, photophysics and photochemistry of nitridorhenium(v) diphosphine complexes and related nitridorhenium(v) organometallics; crystal structure of [RevN(C≡CBut)2(PPh3) 2]
Authors
Issue Date1996
Citation
Journal Of The Chemical Society - Dalton Transactions, 1996 n. 6, p. 1125-1132 How to Cite?
AbstractA series of nitrido complexes [ReNL2X]n+ [L = dppe(Ph2PCH2CH2PPh2), X = F, Cl, Br, NCS, NCO or N3 (n = 1) or MeCN (n = 2); L = dppbz(Ph2PC6H4PPh2-o), X = Cl (n = 1) or MeCN (n = 2)] have been synthesized and shown to exhibit long-lived photoluminescence in both the solid state and fluid solution, derived from the [(dxy)1(dπ*)1] triplet (dπ* = dxy, dyz). The positions of the d-d absorption and emission bands have been found to be dependent on the identity of X. The luminescence quantum yields of [ReNL2-(MeCN)]2+ are greatly enhanced with respect to their chloro analogues. Cyclic voltammetric studies show that the [ReNL2X]+ complexes display an irreversible reduction couple at Epc of ca. -2.0 to -2.3 V and an irreversible oxidation couple at Epa of ca. +1.3 to +1.9 V vs. the ferrocenium-ferrocene couple in MeCN (0.1 mol dm-3 NBu4PF6). An additional irreversible reduction couple is observed at ca. -1.67 and -1.63 V for [ReN(dppe)2(MeCN)]2+ and [ReN(dppbz)2(MeCN)]2+ , respectively. The reactivities of the nitrido complexes toward trifluoroacetic acid and electron donors such as alkoxybenzenes and organic amines have been investigated by Stern-Volmer quenching experiments and transient absorption difference spectroscopy. The electrochemical and spectroscopic properties of [ReNL2X]n+ have been compared with those of organorhenium(v) nitrido complexes [ReNR2(PPh3)2] (R = C≡CBut or C6H4Me-p). The crystal structure of [ReN(C≡CBut)2(PPh3)2] has been determined: monoclinic, space group P21/n, a = 13.708(8), b = 19.161(6), c = 17.246(3) Å, β = 109.49(4)°, U = 4270(3) Å, Z = 4. A Re≡N distance of 1.63(2) Å has been measured.
Persistent Identifierhttp://hdl.handle.net/10722/168036
ISSN
1999 Impact Factor: 2.31
References

 

DC FieldValueLanguage
dc.contributor.authorYam, VWWen_US
dc.contributor.authorTam, KKen_US
dc.contributor.authorCheung, KKen_US
dc.date.accessioned2012-10-08T03:14:25Z-
dc.date.available2012-10-08T03:14:25Z-
dc.date.issued1996en_US
dc.identifier.citationJournal Of The Chemical Society - Dalton Transactions, 1996 n. 6, p. 1125-1132en_US
dc.identifier.issn0300-9246en_US
dc.identifier.urihttp://hdl.handle.net/10722/168036-
dc.description.abstractA series of nitrido complexes [ReNL2X]n+ [L = dppe(Ph2PCH2CH2PPh2), X = F, Cl, Br, NCS, NCO or N3 (n = 1) or MeCN (n = 2); L = dppbz(Ph2PC6H4PPh2-o), X = Cl (n = 1) or MeCN (n = 2)] have been synthesized and shown to exhibit long-lived photoluminescence in both the solid state and fluid solution, derived from the [(dxy)1(dπ*)1] triplet (dπ* = dxy, dyz). The positions of the d-d absorption and emission bands have been found to be dependent on the identity of X. The luminescence quantum yields of [ReNL2-(MeCN)]2+ are greatly enhanced with respect to their chloro analogues. Cyclic voltammetric studies show that the [ReNL2X]+ complexes display an irreversible reduction couple at Epc of ca. -2.0 to -2.3 V and an irreversible oxidation couple at Epa of ca. +1.3 to +1.9 V vs. the ferrocenium-ferrocene couple in MeCN (0.1 mol dm-3 NBu4PF6). An additional irreversible reduction couple is observed at ca. -1.67 and -1.63 V for [ReN(dppe)2(MeCN)]2+ and [ReN(dppbz)2(MeCN)]2+ , respectively. The reactivities of the nitrido complexes toward trifluoroacetic acid and electron donors such as alkoxybenzenes and organic amines have been investigated by Stern-Volmer quenching experiments and transient absorption difference spectroscopy. The electrochemical and spectroscopic properties of [ReNL2X]n+ have been compared with those of organorhenium(v) nitrido complexes [ReNR2(PPh3)2] (R = C≡CBut or C6H4Me-p). The crystal structure of [ReN(C≡CBut)2(PPh3)2] has been determined: monoclinic, space group P21/n, a = 13.708(8), b = 19.161(6), c = 17.246(3) Å, β = 109.49(4)°, U = 4270(3) Å, Z = 4. A Re≡N distance of 1.63(2) Å has been measured.en_US
dc.languageengen_US
dc.relation.ispartofJournal of the Chemical Society - Dalton Transactionsen_US
dc.titleSyntheses, electrochemistry, photophysics and photochemistry of nitridorhenium(v) diphosphine complexes and related nitridorhenium(v) organometallics; crystal structure of [RevN(C≡CBut)2(PPh3) 2]en_US
dc.typeArticleen_US
dc.identifier.emailYam, VWW:wwyam@hku.hken_US
dc.identifier.authorityYam, VWW=rp00822en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1039/DT9960001125-
dc.identifier.scopuseid_2-s2.0-33748396581en_US
dc.identifier.hkuros15490-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33748396581&selection=ref&src=s&origin=recordpageen_US
dc.identifier.issue6en_US
dc.identifier.spage1125en_US
dc.identifier.epage1132en_US
dc.identifier.scopusauthoridYam, VWW=18539304700en_US
dc.identifier.scopusauthoridTam, KK=14423578400en_US
dc.identifier.scopusauthoridCheung, KK=7402406613en_US

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