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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)
Title | 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) |
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Authors | |
Issue Date | 1986 |
Publisher | American 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? |
Abstract | 1,4,8,12-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 Identifier | http://hdl.handle.net/10722/167261 |
ISSN | 2023 Impact Factor: 4.3 2023 SCImago Journal Rankings: 0.928 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Wong, KY | en_US |
dc.contributor.author | Poon, CK | en_US |
dc.date.accessioned | 2012-10-08T03:04:58Z | - |
dc.date.available | 2012-10-08T03:04:58Z | - |
dc.date.issued | 1986 | en_US |
dc.identifier.citation | Inorganic Chemistry, 1986, v. 25 n. 11, p. 1809-1813 | en_US |
dc.identifier.issn | 0020-1669 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167261 | - |
dc.description.abstract | 1,4,8,12-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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_US |
dc.relation.ispartof | Inorganic Chemistry | en_US |
dc.title | 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) | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ic00231a020 | - |
dc.identifier.scopus | eid_2-s2.0-0000278290 | en_US |
dc.identifier.volume | 25 | en_US |
dc.identifier.issue | 11 | en_US |
dc.identifier.spage | 1809 | en_US |
dc.identifier.epage | 1813 | en_US |
dc.identifier.isi | WOS:A1986C522000020 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Wong, KY=7404760030 | en_US |
dc.identifier.scopusauthorid | Poon, CK=7202673504 | en_US |
dc.identifier.issnl | 0020-1669 | - |