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Article: Bis(amido)ruthenium(IV) complexes with 2,3-diamino-2,3-dimethylbutane. Crystal structure and reversible Ru(IV) - Amide/Ru(III) - Amine and Ru(IV) - Amide/Ru(II)-amine redox couples in aqueous solution

TitleBis(amido)ruthenium(IV) complexes with 2,3-diamino-2,3-dimethylbutane. Crystal structure and reversible Ru(IV) - Amide/Ru(III) - Amine and Ru(IV) - Amide/Ru(II)-amine redox couples in aqueous solution
Authors
Issue Date1996
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1996, v. 35 n. 11, p. 3369-3374 How to Cite?
AbstractTwo bis(amido)ruthenium(IV) complexes, [RuIv(bpy)(L-H)2]2+ and [RuIV(L)(L-H)2]2+ (bpy = 2,2′-bipyridine, L = 2,3-diamino-2,3-dimethylbutane, L-H = (H2NCMe2CMe2NH)-), were prepared by chemical oxidation of [RuII(bpy)(L)2]2+ and the reaction of [(n-Bu)4N][RuvINCl4] with L, respectively. The structures of [Ru(bpy)(L-H)2][ZnBr4]·CH3CN and [Ru(L)(L-H)2]Cl2·2H2O were determined by X-ray crystal analysis. [Ru(bpy)(L-H)2][ZnBr4]·CH3CN crystallizes in the monoclinic space group P21/n with a = 12.597(2) Å, b = 15.909(2) Å, c = 16.785(2) Å, β= 91.74(1)°, and Z = 4. [Ru(L)(L-H)2]Cl2·2H2O crystallizes in the tetragonal space group I41/a with a = 31.892(6) Å, c = 10.819(3) Å, and Z = 16. In both complexes, the two Ru-N(amide) bonds are cis to each other with bond distances ranging from 1.835(7) to 1.856(7) Å. The N(amide)-Ru-N(amide) angles are about 110°. The two Ru(IV) complexes are diamagnetic, and the chemical shifts of the amide protons occur at around 13 ppm. Both complexes display reversible metal-amide/metal-amine redox couples in aqueous solution with a pyrolytic graphite electrode. Depending on the pH of the media, reversible/ quasireversible le--2H+ Ru(IV)-amide/Ru(III)-amine and 2e--2H+ Ru(IV)-amide/Ru(II)-amine redox couples have been observed. At pH = 1.0, the E° is 0.46 V for [RuIv(bPy)(L-H)2]2+/[Ru III(bpy)(L)2]3+ and 0.29 V vs SCE for [RuIV(L)(L-H)2]2+/[RuIII(L) 3]3+. The difference in the E° values for the two Ru(IV)-amide complexes has been attributed to the fact that the chelating saturated diamine ligand is a better σ-donor than 2,2′-bipyridine.
Persistent Identifierhttp://hdl.handle.net/10722/69298
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
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DC FieldValueLanguage
dc.contributor.authorChiu, WHen_HK
dc.contributor.authorPeng, SMen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:12:22Z-
dc.date.available2010-09-06T06:12:22Z-
dc.date.issued1996en_HK
dc.identifier.citationInorganic Chemistry, 1996, v. 35 n. 11, p. 3369-3374en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69298-
dc.description.abstractTwo bis(amido)ruthenium(IV) complexes, [RuIv(bpy)(L-H)2]2+ and [RuIV(L)(L-H)2]2+ (bpy = 2,2′-bipyridine, L = 2,3-diamino-2,3-dimethylbutane, L-H = (H2NCMe2CMe2NH)-), were prepared by chemical oxidation of [RuII(bpy)(L)2]2+ and the reaction of [(n-Bu)4N][RuvINCl4] with L, respectively. The structures of [Ru(bpy)(L-H)2][ZnBr4]·CH3CN and [Ru(L)(L-H)2]Cl2·2H2O were determined by X-ray crystal analysis. [Ru(bpy)(L-H)2][ZnBr4]·CH3CN crystallizes in the monoclinic space group P21/n with a = 12.597(2) Å, b = 15.909(2) Å, c = 16.785(2) Å, β= 91.74(1)°, and Z = 4. [Ru(L)(L-H)2]Cl2·2H2O crystallizes in the tetragonal space group I41/a with a = 31.892(6) Å, c = 10.819(3) Å, and Z = 16. In both complexes, the two Ru-N(amide) bonds are cis to each other with bond distances ranging from 1.835(7) to 1.856(7) Å. The N(amide)-Ru-N(amide) angles are about 110°. The two Ru(IV) complexes are diamagnetic, and the chemical shifts of the amide protons occur at around 13 ppm. Both complexes display reversible metal-amide/metal-amine redox couples in aqueous solution with a pyrolytic graphite electrode. Depending on the pH of the media, reversible/ quasireversible le--2H+ Ru(IV)-amide/Ru(III)-amine and 2e--2H+ Ru(IV)-amide/Ru(II)-amine redox couples have been observed. At pH = 1.0, the E° is 0.46 V for [RuIv(bPy)(L-H)2]2+/[Ru III(bpy)(L)2]3+ and 0.29 V vs SCE for [RuIV(L)(L-H)2]2+/[RuIII(L) 3]3+. The difference in the E° values for the two Ru(IV)-amide complexes has been attributed to the fact that the chelating saturated diamine ligand is a better σ-donor than 2,2′-bipyridine.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleBis(amido)ruthenium(IV) complexes with 2,3-diamino-2,3-dimethylbutane. Crystal structure and reversible Ru(IV) - Amide/Ru(III) - Amine and Ru(IV) - Amide/Ru(II)-amine redox couples in aqueous solutionen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=35&spage=3369&epage=3374&date=1996&atitle=Bis(amido)ruthenium(IV)+complexes+with+2,3-diamino-2,3-dimethylbutane.++Crystal+structure+and+reversible+Ru(IV)-Amide/Ru(III)-Amine+and+Ru(IV)-Amide/Ru(II)-Amine+redox+couples+in+aqueous+solutionen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic951145n-
dc.identifier.pmid11666540-
dc.identifier.scopuseid_2-s2.0-0000970528en_HK
dc.identifier.hkuros22008en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000970528&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume35en_HK
dc.identifier.issue11en_HK
dc.identifier.spage3369en_HK
dc.identifier.epage3374en_HK
dc.identifier.isiWOS:A1996UM69300043-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChiu, WH=7201503487en_HK
dc.identifier.scopusauthoridPeng, SM=35464852200en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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