File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Stabilization of transition-metal complexes in high oxidation states by macrocyclic tertiary amines. Electrochemical generation and spectroscopic properties of novel dihalogeno and pseudohalogeno tetraamine complexes of ruthenium(IV)

TitleStabilization of transition-metal complexes in high oxidation states by macrocyclic tertiary amines. Electrochemical generation and spectroscopic properties of novel dihalogeno and pseudohalogeno tetraamine complexes of ruthenium(IV)
Authors
Issue Date1986
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1986, v. 25 n. 11, p. 1809-1813 How to Cite?
Abstract1,4,8,12-Tetramethyl-1,4,8,12-tetraazacyclopentadecane (15-TMC) was synthesized by the reaction of 1,4,8,12-tetraazacyclopentadecane with formaldehyde. Reactions of K2[RuCl5H2O] with 15-TMC and 16-TMC (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) in ethanol yielded trans-[RuLCl2]Cl (L = 15-TMC and 16-TMC, respectively) in high yields. The syntheses of trans-[RuLBr2]ClO4 [L = (TMEA)2 (TMEA = N,N,N′,N′-tetramethyl-1,2-ethanediamine), 14-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and 15-TMC], trans-[Ru(TMEA)2(NCS)2]NCS, and trans-[Ru(14-TMC)(CH3CN)2][ClO4]2 are also described. The electrochemistry of trans-[RuLX2]+ [L = (TMEA)2, 14-TMC, 15-TMC, and 16-TMC; X = Cl, Br, and NCO] in acetonitrile were examined. The Ef° values of trans-[RuLCl2]Cl in 2 M HCl have been found to decrease with L in the order 14-TMC > 15-TMC > 16-TMC. Reversible/quasi-reversible Ru(IV)/Ru(III) couples in acetonitrile with Ef° values ranging from 1.05 to 1.27 V vs. the ferrocene couple were observed. Controlled-potential electrolyses of trans-[RuLX2]+ at 1.30 V vs. the ferrocene couple generated some novel trans-[RuIVLX2]2+ complexes. The ligand-to-metal charge-transfer transitions in the UV-vis spectra of trans-[RuIV(TMEA)2X2]2+ have been identified at 410 (X = Cl) and 570 nm (X = Br), which are considerably red-shifted with respect to their Ru(III) counterparts. © 1986 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167261
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorWong, KYen_US
dc.contributor.authorPoon, CKen_US
dc.date.accessioned2012-10-08T03:04:58Z-
dc.date.available2012-10-08T03:04:58Z-
dc.date.issued1986en_US
dc.identifier.citationInorganic Chemistry, 1986, v. 25 n. 11, p. 1809-1813en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167261-
dc.description.abstract1,4,8,12-Tetramethyl-1,4,8,12-tetraazacyclopentadecane (15-TMC) was synthesized by the reaction of 1,4,8,12-tetraazacyclopentadecane with formaldehyde. Reactions of K2[RuCl5H2O] with 15-TMC and 16-TMC (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) in ethanol yielded trans-[RuLCl2]Cl (L = 15-TMC and 16-TMC, respectively) in high yields. The syntheses of trans-[RuLBr2]ClO4 [L = (TMEA)2 (TMEA = N,N,N′,N′-tetramethyl-1,2-ethanediamine), 14-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and 15-TMC], trans-[Ru(TMEA)2(NCS)2]NCS, and trans-[Ru(14-TMC)(CH3CN)2][ClO4]2 are also described. The electrochemistry of trans-[RuLX2]+ [L = (TMEA)2, 14-TMC, 15-TMC, and 16-TMC; X = Cl, Br, and NCO] in acetonitrile were examined. The Ef° values of trans-[RuLCl2]Cl in 2 M HCl have been found to decrease with L in the order 14-TMC > 15-TMC > 16-TMC. Reversible/quasi-reversible Ru(IV)/Ru(III) couples in acetonitrile with Ef° values ranging from 1.05 to 1.27 V vs. the ferrocene couple were observed. Controlled-potential electrolyses of trans-[RuLX2]+ at 1.30 V vs. the ferrocene couple generated some novel trans-[RuIVLX2]2+ complexes. The ligand-to-metal charge-transfer transitions in the UV-vis spectra of trans-[RuIV(TMEA)2X2]2+ have been identified at 410 (X = Cl) and 570 nm (X = Br), which are considerably red-shifted with respect to their Ru(III) counterparts. © 1986 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleStabilization of transition-metal complexes in high oxidation states by macrocyclic tertiary amines. Electrochemical generation and spectroscopic properties of novel dihalogeno and pseudohalogeno tetraamine complexes of ruthenium(IV)en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic00231a020-
dc.identifier.scopuseid_2-s2.0-0000278290en_US
dc.identifier.volume25en_US
dc.identifier.issue11en_US
dc.identifier.spage1809en_US
dc.identifier.epage1813en_US
dc.identifier.isiWOS:A1986C522000020-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridWong, KY=7404760030en_US
dc.identifier.scopusauthoridPoon, CK=7202673504en_US

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats