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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]
Title | Syntheses, electrochemistry, photophysics and photochemistry of nitridorhenium(v) diphosphine complexes and related nitridorhenium(v) organometallics; crystal structure of [RevN(C≡CBut)2(PPh3) 2] |
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Authors | |
Issue Date | 1996 |
Citation | Journal Of The Chemical Society - Dalton Transactions, 1996 n. 6, p. 1125-1132 How to Cite? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/168036 |
ISSN | |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Yam, VWW | en_US |
dc.contributor.author | Tam, KK | en_US |
dc.contributor.author | Cheung, KK | en_US |
dc.date.accessioned | 2012-10-08T03:14:25Z | - |
dc.date.available | 2012-10-08T03:14:25Z | - |
dc.date.issued | 1996 | en_US |
dc.identifier.citation | Journal Of The Chemical Society - Dalton Transactions, 1996 n. 6, p. 1125-1132 | en_US |
dc.identifier.issn | 0300-9246 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168036 | - |
dc.description.abstract | A 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.language | eng | en_US |
dc.relation.ispartof | Journal of the Chemical Society - Dalton Transactions | en_US |
dc.title | Syntheses, 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.type | Article | en_US |
dc.identifier.email | Yam, VWW:wwyam@hku.hk | en_US |
dc.identifier.authority | Yam, VWW=rp00822 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1039/DT9960001125 | - |
dc.identifier.scopus | eid_2-s2.0-33748396581 | en_US |
dc.identifier.hkuros | 15490 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-33748396581&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.issue | 6 | en_US |
dc.identifier.spage | 1125 | en_US |
dc.identifier.epage | 1132 | en_US |
dc.identifier.isi | WOS:A1996UC26200041 | - |
dc.identifier.scopusauthorid | Yam, VWW=18539304700 | en_US |
dc.identifier.scopusauthorid | Tam, KK=14423578400 | en_US |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_US |
dc.identifier.issnl | 0300-9246 | - |