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Article: Rhenium(VII) and -(V) imido and oxo complexes containing 1,4,7-triazacyclononane: Synthesis, electrochemistry and crystal structures

TitleRhenium(VII) and -(V) imido and oxo complexes containing 1,4,7-triazacyclononane: Synthesis, electrochemistry and crystal structures
Authors
KeywordsAzamacrocycle complexes
Crystal structures
Electrochemisiry
Imido complexes
Rhenium complexes
Issue Date1998
PublisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/ica
Citation
Inorganica Chimica Acta, 1998, v. 272 n. 1-2, p. 176-187 How to Cite?
AbstractA new class of cationic rhenium(VII) imido and oxo complexes wilh the macrocyclic ligand 1,4,7-triazacyclononane (L) was prepared. Depending on the reaction conditions, [(L - H)Re(N tBu)2(OSiMe3)]+ (1) [(L-H) denotes deprotonation at N], [LRe(N tBu)2O] (2) and/or [LRe(N tBu)2(NH tBu)]2+ (4) can be obtained by the treatment of Re(N tBu)3(OSiMe3) with L. Reaction of 2·BPh4 with trifluoromethanesulfonic anhydride gives [(L - H)Re(N tBu)2(CF3SO3)]BPh4 (3-BPh4). Interaction of [Re(N tBu)2 (OSiMe3)(μ-O)]2 with L yields [LRe(N tBu)O2]+ (5). In contrast to the t-butylimido analogues, only [LRe(NAr)2O]Cl (6·Cl) is isolated from the reaction of Re(NAr)3Cl with excess L. Complexes 2, 5 and 6 are stable in 0.1 M CF3CO2H. Electrochemically, they undergo proton-coupled two electron reductions at pH 1 with Epc; (cathodic peak potential) of -0.30. -0.29 and -0.12 V versus SCE respectively. Constant potential electrolysis of 6 at -0.3 V affords a green solution which is rapidly oxidised in air to give [LRe(NAr)O2]+ (7). The reduction of 5-ClO4 by zinc in the presence of oxalic acid and CF3CO2H affords the rhenium(V) species [LRe(N tBu)(oxalate)]ClO4 (8·ClO4) and [LRe(N tBu)(CF3CO2)2]ClO4 (9·ClO4) respectively. The molecular structures of 2·ClO4,3·BPh4, 5·ClO4, 6·Cl·2H2O. and 8·ClO4 have been determined by X-ray crystal analysis. The Re-N(L) bonds which are trans to imido and oxo ligands are comparatively long (2.344-2.243 Å). The range of Re-N(imido) and Re-O(oxo) distances (1.67-1.78 Å and 1.71-1.76 Å respectively) can be rationalised by the oxo/imido ligand ratio in the Re(VII) complexes. © 1998 Elsevier Science S.A. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/69783
ISSN
2015 Impact Factor: 1.918
2015 SCImago Journal Rankings: 0.584
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorCheng, JYKen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorWong, KYen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:16:48Z-
dc.date.available2010-09-06T06:16:48Z-
dc.date.issued1998en_HK
dc.identifier.citationInorganica Chimica Acta, 1998, v. 272 n. 1-2, p. 176-187en_HK
dc.identifier.issn0020-1693en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69783-
dc.description.abstractA new class of cationic rhenium(VII) imido and oxo complexes wilh the macrocyclic ligand 1,4,7-triazacyclononane (L) was prepared. Depending on the reaction conditions, [(L - H)Re(N tBu)2(OSiMe3)]+ (1) [(L-H) denotes deprotonation at N], [LRe(N tBu)2O] (2) and/or [LRe(N tBu)2(NH tBu)]2+ (4) can be obtained by the treatment of Re(N tBu)3(OSiMe3) with L. Reaction of 2·BPh4 with trifluoromethanesulfonic anhydride gives [(L - H)Re(N tBu)2(CF3SO3)]BPh4 (3-BPh4). Interaction of [Re(N tBu)2 (OSiMe3)(μ-O)]2 with L yields [LRe(N tBu)O2]+ (5). In contrast to the t-butylimido analogues, only [LRe(NAr)2O]Cl (6·Cl) is isolated from the reaction of Re(NAr)3Cl with excess L. Complexes 2, 5 and 6 are stable in 0.1 M CF3CO2H. Electrochemically, they undergo proton-coupled two electron reductions at pH 1 with Epc; (cathodic peak potential) of -0.30. -0.29 and -0.12 V versus SCE respectively. Constant potential electrolysis of 6 at -0.3 V affords a green solution which is rapidly oxidised in air to give [LRe(NAr)O2]+ (7). The reduction of 5-ClO4 by zinc in the presence of oxalic acid and CF3CO2H affords the rhenium(V) species [LRe(N tBu)(oxalate)]ClO4 (8·ClO4) and [LRe(N tBu)(CF3CO2)2]ClO4 (9·ClO4) respectively. The molecular structures of 2·ClO4,3·BPh4, 5·ClO4, 6·Cl·2H2O. and 8·ClO4 have been determined by X-ray crystal analysis. The Re-N(L) bonds which are trans to imido and oxo ligands are comparatively long (2.344-2.243 Å). The range of Re-N(imido) and Re-O(oxo) distances (1.67-1.78 Å and 1.71-1.76 Å respectively) can be rationalised by the oxo/imido ligand ratio in the Re(VII) complexes. © 1998 Elsevier Science S.A. All rights reserved.en_HK
dc.languageengen_HK
dc.publisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/icaen_HK
dc.relation.ispartofInorganica Chimica Actaen_HK
dc.rightsInorganica Chimica Acta. Copyright © Elsevier BV.en_HK
dc.subjectAzamacrocycle complexesen_HK
dc.subjectCrystal structuresen_HK
dc.subjectElectrochemisiryen_HK
dc.subjectImido complexesen_HK
dc.subjectRhenium complexesen_HK
dc.titleRhenium(VII) and -(V) imido and oxo complexes containing 1,4,7-triazacyclononane: Synthesis, electrochemistry and crystal structuresen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1693&volume=272&spage=176&epage=187&date=1998&atitle=Rhenium(VII)+and+-(V)+imido+and+oxo+complexes+containing+1,4,7-triazacyclononane:++synthesis,+electrochemistry+and+crystal+structuresen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/S0020-1693(97)05936-7-
dc.identifier.scopuseid_2-s2.0-0038368375en_HK
dc.identifier.hkuros32044en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0038368375&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume272en_HK
dc.identifier.issue1-2en_HK
dc.identifier.spage176en_HK
dc.identifier.epage187en_HK
dc.identifier.isiWOS:000073056500027-
dc.publisher.placeNetherlandsen_HK
dc.identifier.scopusauthoridCheng, JYK=7405940807en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridWong, KY=7404760030en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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