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Article: Synthetic, structural and electrochemical studies of cationic chromium(VI) and molybdenum(VI) bis(imido) complexes supported by 1,4,7-triazacyclononane macrocycles

TitleSynthetic, structural and electrochemical studies of cationic chromium(VI) and molybdenum(VI) bis(imido) complexes supported by 1,4,7-triazacyclononane macrocycles
Authors
Issue Date1999
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, 1999 n. 18, p. 3197-3201 How to Cite?
AbstractTreatment of [Cr(NtBu)2Cl2] or [Mo(NtBu)2Cl2(dme)] with 1,4,7-triazacyclononane (tacn) in THF, followed by metathesis using NaClO4 in aqueous medium, readily afforded [M(tacn)(NtBu)2Cl]ClO4 (M = Cr 1 or Mo 2); [M(Me3tacn)(NtBu)2Cl]Cl (M = Cr 3 or Mo 4) were similarly prepared using the metal precursors and 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn). Complexes 1-4 are resistant to hydrolysis, but do not mediate imido group transfer reactions. Distinctive UV-vis absorption bands are tentatively assigned to imido-to-metal LMCT transitions. The crystal structures of 1 and 2·CH3CN show that the 3 nitrogen atoms of tacn are not equidistant from the respective metal centres. A severely distorted imido moiety (imido angle 151.8(4)°) has been observed in the structure of 1 but not 2·CH3CN, and is attributed to steric and crystal packing factors rather than electronic effects. Metathesis of both chloride groups in 3 using AgOTf(OTf = SO3CF3) yielded [Cr(Me3tacn)(NtBu)2(OTf)]OTf 5. The cyclic voltammograms of 1-5 in acetonitrile consist of a quasi-reversible couple (+0.86 to +1.20 V vs. Cp2Fe0/+) and an irreversible wave (-1.04 to -2.08 V vs. Cp2Fe0/+); the former couple is assigned to an imido-centred oxidation. © The Royal Society of Chemistry 1999.
Persistent Identifierhttp://hdl.handle.net/10722/69151
ISSN
1999 Impact Factor: 2.31
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorLee, FWen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:11:02Z-
dc.date.available2010-09-06T06:11:02Z-
dc.date.issued1999en_HK
dc.identifier.citationJournal Of The Chemical Society - Dalton Transactions, 1999 n. 18, p. 3197-3201en_HK
dc.identifier.issn0300-9246en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69151-
dc.description.abstractTreatment of [Cr(NtBu)2Cl2] or [Mo(NtBu)2Cl2(dme)] with 1,4,7-triazacyclononane (tacn) in THF, followed by metathesis using NaClO4 in aqueous medium, readily afforded [M(tacn)(NtBu)2Cl]ClO4 (M = Cr 1 or Mo 2); [M(Me3tacn)(NtBu)2Cl]Cl (M = Cr 3 or Mo 4) were similarly prepared using the metal precursors and 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn). Complexes 1-4 are resistant to hydrolysis, but do not mediate imido group transfer reactions. Distinctive UV-vis absorption bands are tentatively assigned to imido-to-metal LMCT transitions. The crystal structures of 1 and 2·CH3CN show that the 3 nitrogen atoms of tacn are not equidistant from the respective metal centres. A severely distorted imido moiety (imido angle 151.8(4)°) has been observed in the structure of 1 but not 2·CH3CN, and is attributed to steric and crystal packing factors rather than electronic effects. Metathesis of both chloride groups in 3 using AgOTf(OTf = SO3CF3) yielded [Cr(Me3tacn)(NtBu)2(OTf)]OTf 5. The cyclic voltammograms of 1-5 in acetonitrile consist of a quasi-reversible couple (+0.86 to +1.20 V vs. Cp2Fe0/+) and an irreversible wave (-1.04 to -2.08 V vs. Cp2Fe0/+); the former couple is assigned to an imido-centred oxidation. © The Royal Society of Chemistry 1999.en_HK
dc.languageengen_HK
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofJournal of the Chemical Society - Dalton Transactionsen_HK
dc.titleSynthetic, structural and electrochemical studies of cationic chromium(VI) and molybdenum(VI) bis(imido) complexes supported by 1,4,7-triazacyclononane macrocyclesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=3197&epage=3201&date=1999&atitle=Synthetic,+structural+and+electrochemical+studies+of+cationic+chromium(VI)+and+molybdenum(VI)+bis(imido)+complexes+supported+by+1,4,7-triazacyclononane+macrocyclesen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/A904191E-
dc.identifier.scopuseid_2-s2.0-33749086929en_HK
dc.identifier.hkuros51130en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33749086929&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue18en_HK
dc.identifier.spage3197en_HK
dc.identifier.epage3201en_HK
dc.identifier.isiWOS:000082425600011-
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridLee, FW=7403111574en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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