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Article: Novel ruthenium-oxo complexes of saturated macrocycles with nitrogen and oxygen donors and X-ray crystal structure of trans-[RuIV(L)O(H2O)][ClO4]2

TitleNovel ruthenium-oxo complexes of saturated macrocycles with nitrogen and oxygen donors and X-ray crystal structure of trans-[RuIV(L)O(H2O)][ClO4]2
Authors
Issue Date1989
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 1989, v. 111 n. 25, p. 9048-9056 How to Cite?
AbstractReaction of K2[RuCl5(H2O)] with L (1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) in refluxing ethanol yielded trans-[RuIII(L)Cl2]2+, isolated as chloride salt. Treatment of trans-[RuIII(L)Cl2]+ with Ag+ in water led to the formation of trans-[RuIII(L)(OH)(H2O)]2+, which could be oxidized to trans-[RuIV(L)O(H2O)]2+ and trans-[RuVI(L)(O)2]2+ by electrochemical and Ce(IV) oxidation, respectively. Magnetic susceptibility measurements on the perchlorate salts of trans-[RuIII(L)(OH)(H2O)]2+, trans-[RuIV(L)(O)(H2O)]2+, and trans-[RuVI(L)(O)2]2+ showed that their μeff values are 1.86, 2.87, and 0 μB, respectively, in accordance to their electronic formulation [Ru(III), (dxy)2(dxz + dyz)2(dxz - dyz)1; Ru(IV), (dxy)2(dxz)1(dyz) 1; Ru(VI), (dxy)2]. The Ru=O stretching frequencies for the Ru(IV) and Ru(VI) complexes are 845 and 865 cm-1. The X-ray crystal structure of trans-[RuIV(L)(O)(H2O)][ClO4] 2·2H2O has been determined: C21H34N2Cl2O14Ru; Mr 710.47; triclinic, space group P1; a = 11.157 (5), b = 11.697 (3), c = 12.598 (2) Å; α = 74.05 (1), β = 61.55 (2), γ = 71.33 (2)°; V 1354.7 Å3; Z = 2; 4calcd = 1.742, dmeasd = 1.72 g cm-3; μ(MO Kα) = 8.4 cm-1. The coordinated oxo and aquo groups are trans to each other. The measured Ru=O distance of 1.739 (2) Å is the shortest one ever reported for oxoruthenium(IV) complexes. The intermolecular separation of two Ru=O moieties is 2.8 Å, which features significant nonbonded [Ru=O⋯O=Ru] interaction. At pH = 1.1, the E1/2 values for the trans-[RuVI(L)(O)2]2+/trans-[Ru IV(L)(O)(H2O)]2+ and trans-[RuIV(L)O(H2O)]2+/trans-[Ru III(L)(OH)(H2O)]2+ couples are, respectively, 0.92 and 0.58 V vs SCE. Thus, trans-[RuVI(L)(O)2]2+ is a powerful oxidant and is 0.26 V more oxidizing than trans-[RuVI(TMC)(O)2]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). trans-[RuVI(L)(O)2]2+ is capable of oxidizing a wide variety of organic substrates, including alcohols, olefins, aromatic hydrocarbons, and adamantane under mild conditions. Electrocatalytic oxidation of benzyl alcohol and oxidation of organic substrates with PhIO are achieved with the [RuIII(L)(OH)(H2O)]2+ or [RuIV(L)(O)(H2O)]2+ complex as catalyst. © 1989 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167484
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_HK
dc.contributor.authorTang, WTen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLai, TFen_HK
dc.date.accessioned2012-10-08T03:07:33Z-
dc.date.available2012-10-08T03:07:33Z-
dc.date.issued1989en_HK
dc.identifier.citationJournal Of The American Chemical Society, 1989, v. 111 n. 25, p. 9048-9056en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167484-
dc.description.abstractReaction of K2[RuCl5(H2O)] with L (1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) in refluxing ethanol yielded trans-[RuIII(L)Cl2]2+, isolated as chloride salt. Treatment of trans-[RuIII(L)Cl2]+ with Ag+ in water led to the formation of trans-[RuIII(L)(OH)(H2O)]2+, which could be oxidized to trans-[RuIV(L)O(H2O)]2+ and trans-[RuVI(L)(O)2]2+ by electrochemical and Ce(IV) oxidation, respectively. Magnetic susceptibility measurements on the perchlorate salts of trans-[RuIII(L)(OH)(H2O)]2+, trans-[RuIV(L)(O)(H2O)]2+, and trans-[RuVI(L)(O)2]2+ showed that their μeff values are 1.86, 2.87, and 0 μB, respectively, in accordance to their electronic formulation [Ru(III), (dxy)2(dxz + dyz)2(dxz - dyz)1; Ru(IV), (dxy)2(dxz)1(dyz) 1; Ru(VI), (dxy)2]. The Ru=O stretching frequencies for the Ru(IV) and Ru(VI) complexes are 845 and 865 cm-1. The X-ray crystal structure of trans-[RuIV(L)(O)(H2O)][ClO4] 2·2H2O has been determined: C21H34N2Cl2O14Ru; Mr 710.47; triclinic, space group P1; a = 11.157 (5), b = 11.697 (3), c = 12.598 (2) Å; α = 74.05 (1), β = 61.55 (2), γ = 71.33 (2)°; V 1354.7 Å3; Z = 2; 4calcd = 1.742, dmeasd = 1.72 g cm-3; μ(MO Kα) = 8.4 cm-1. The coordinated oxo and aquo groups are trans to each other. The measured Ru=O distance of 1.739 (2) Å is the shortest one ever reported for oxoruthenium(IV) complexes. The intermolecular separation of two Ru=O moieties is 2.8 Å, which features significant nonbonded [Ru=O⋯O=Ru] interaction. At pH = 1.1, the E1/2 values for the trans-[RuVI(L)(O)2]2+/trans-[Ru IV(L)(O)(H2O)]2+ and trans-[RuIV(L)O(H2O)]2+/trans-[Ru III(L)(OH)(H2O)]2+ couples are, respectively, 0.92 and 0.58 V vs SCE. Thus, trans-[RuVI(L)(O)2]2+ is a powerful oxidant and is 0.26 V more oxidizing than trans-[RuVI(TMC)(O)2]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). trans-[RuVI(L)(O)2]2+ is capable of oxidizing a wide variety of organic substrates, including alcohols, olefins, aromatic hydrocarbons, and adamantane under mild conditions. Electrocatalytic oxidation of benzyl alcohol and oxidation of organic substrates with PhIO are achieved with the [RuIII(L)(OH)(H2O)]2+ or [RuIV(L)(O)(H2O)]2+ complex as catalyst. © 1989 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titleNovel ruthenium-oxo complexes of saturated macrocycles with nitrogen and oxygen donors and X-ray crystal structure of trans-[RuIV(L)O(H2O)][ClO4]2en_HK
dc.typeArticleen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja00207a010-
dc.identifier.scopuseid_2-s2.0-0024846074en_HK
dc.identifier.volume111en_HK
dc.identifier.issue25en_HK
dc.identifier.spage9048en_HK
dc.identifier.epage9056en_HK
dc.identifier.isiWOS:A1989CC64600010-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridTang, WT=15121154000en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridLai, TF=36793788300en_HK

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