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Article: Synthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η5-C5Me5)Re(NO)(PR3)(CH3): in search of radical cations with enhanced kinetic stabilities

TitleSynthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η5-C5Me5)Re(NO)(PR3)(CH3): in search of radical cations with enhanced kinetic stabilities
Authors
KeywordsRhenium
Radical cations
Cyclic voltammetry
ESR
TCNE
Issue Date2000
PublisherElsevier SA. The Journal's web site is located at http://www.elsevier.com/locate/jorganchem
Citation
Journal of Organometallic Chemistry, 2000, v. 616 n. 1-2, p. 44-53 How to Cite?
AbstractReactions of racemic [(η5-C5Me5)Re(NO)(NCCH3)(CO)]+ BF4− and phosphines PR3 (R=C6H5a; 4-C6H4CH3b; 4-C6H4-t-C4H9c; 4-C6H4C6H5d; 4-C6H4OCH3e; c-C6H11f) give the phosphine carbonyl complexes [(η5-C5Me5)Re(NO)(PR3)(CO)]+ BF4− (5a–5f+ BF4−; 55–95%). These are treated with LiEt3BH and then BH3·THF to give the phosphine methyl complexes (η5-C5Me5)Re(NO)(PR3)(CH3) (2a–2f, 50–86%). Cyclic voltammetry shows that the new compounds 2b–2f undergo chemically reversible one-electron oxidations that are thermodynamically more favorable than that of 2a (ΔE°=0.07, 0.07, 0.01, 0.09, 0.22 V; CH2Cl2). The radical cations 2+ X− can be generated with Ag+ X− or (η5-C5H5)2Fe+ X− (X−=PF6−, SbF6−), as evidenced by IR and ESR spectra, but are labile and efforts to isolate pure salts fail. Reaction of 2a and TCNE give (η5-C5Me5)Re(NO)(η2-TCNE)(CH3), which is crystallographically characterized and proposed to form by initial electron transfer followed by radical chain substitution.
Persistent Identifierhttp://hdl.handle.net/10722/70338
ISSN
2015 Impact Factor: 2.336
2015 SCImago Journal Rankings: 0.732
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorMeyer, WEen_HK
dc.contributor.authorAmoroso, AJen_HK
dc.contributor.authorJaeger, Men_HK
dc.contributor.authorLe Bras, Jen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorGladysz, JAen_HK
dc.date.accessioned2010-09-06T06:21:56Z-
dc.date.available2010-09-06T06:21:56Z-
dc.date.issued2000en_HK
dc.identifier.citationJournal of Organometallic Chemistry, 2000, v. 616 n. 1-2, p. 44-53en_HK
dc.identifier.issn0022-328Xen_HK
dc.identifier.urihttp://hdl.handle.net/10722/70338-
dc.description.abstractReactions of racemic [(η5-C5Me5)Re(NO)(NCCH3)(CO)]+ BF4− and phosphines PR3 (R=C6H5a; 4-C6H4CH3b; 4-C6H4-t-C4H9c; 4-C6H4C6H5d; 4-C6H4OCH3e; c-C6H11f) give the phosphine carbonyl complexes [(η5-C5Me5)Re(NO)(PR3)(CO)]+ BF4− (5a–5f+ BF4−; 55–95%). These are treated with LiEt3BH and then BH3·THF to give the phosphine methyl complexes (η5-C5Me5)Re(NO)(PR3)(CH3) (2a–2f, 50–86%). Cyclic voltammetry shows that the new compounds 2b–2f undergo chemically reversible one-electron oxidations that are thermodynamically more favorable than that of 2a (ΔE°=0.07, 0.07, 0.01, 0.09, 0.22 V; CH2Cl2). The radical cations 2+ X− can be generated with Ag+ X− or (η5-C5H5)2Fe+ X− (X−=PF6−, SbF6−), as evidenced by IR and ESR spectra, but are labile and efforts to isolate pure salts fail. Reaction of 2a and TCNE give (η5-C5Me5)Re(NO)(η2-TCNE)(CH3), which is crystallographically characterized and proposed to form by initial electron transfer followed by radical chain substitution.-
dc.languageengen_HK
dc.publisherElsevier SA. The Journal's web site is located at http://www.elsevier.com/locate/jorganchemen_HK
dc.relation.ispartofJournal of Organometallic Chemistryen_HK
dc.subjectRhenium-
dc.subjectRadical cations-
dc.subjectCyclic voltammetry-
dc.subjectESR-
dc.subjectTCNE-
dc.titleSynthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η5-C5Me5)Re(NO)(PR3)(CH3): in search of radical cations with enhanced kinetic stabilitiesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0022-328X&volume=616&spage=44&epage=53&date=2000&atitle=Synthesis+and+oxidation+of+chiral+rhenium+phosphine+methyl+complexes+of+the+formula+(h5-C5Me5)Re(NO)(PR3)(CH3):+in+search+of+radical+cations+with+enhanced+kinetic+stabilitiesen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1016/S0022-328X(00)00528-3-
dc.identifier.hkuros56701en_HK
dc.identifier.volume616-
dc.identifier.issue1-2-
dc.identifier.spage44-
dc.identifier.epage53-
dc.identifier.isiWOS:000166128700006-
dc.publisher.placeSwitzerland-

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