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Article: Oxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II)

TitleOxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II)
Authors
Issue Date1997
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1997, v. 36 n. 20, p. 4432-4437 How to Cite?
AbstractThe reaction of Ru(Et2dtc)2(DMSO)2 (Et2dtc = N,N-diethyldithiocarbamate; DMSO = dimethyl sulfoxide) with t-BuNC gave trans-Ru(Et2dtc)2(CN-t-Bu)2, 1. Complex 1 crystallizes in the monoclinic space group P21/n with a = 9.753(2) Å, b = 11.583(2) Å, c = 12.974(2) Å, and β = 91.8(2)° for Z = 2. The crystal structure of 1 shows the trans disposition of the two isocyanides; the mean Ru-S and Ru-C distances are 2.409 and 1.977(2) Å, respectively. Treatment of [Ru(diene)Cl2]n with Na(Et2dtc) afforded Ru(Et2dtc)2(diene) (diene = bicyclo[2.2.1]-hepta-2,5-diene (NBD), 2, 1,5-cyclooctadiene (COD), 3). Complex 2 crystallizes in the triclinic space group P1̄ with a = 7.316(1) Å, b = 10.346(1) Å, c = 15.123(2) Å, a = 103.69(2)°, β= 93.54(2)°, and γ = 100.61(2)° for Z = 2. The mean Ru-S and Ru-C distances in 2 are 2.416 and 2.137 Å, respectively. The reaction of cis-Ru(Et2dtc)2(CO)2 with iodine gave the 2:1 molecular iodine complex cis-Ru(Et2dtc)2(CO)2·1/2I2 4, which crystallizes in the monoclinic space group P21/c with a 7.347(2), b = 22.227(2) Å, c = 12.891(2) Å, and β =95.98 (2)° for Z = 4. The mean Ru-S and Ru-C and the I-I distances in complex 4 are 2.427, 1.903, and 2.745(1) Å, respectively. Treatment of Ru(Et2dtc)2(DMSO)2 with I2 gave the linear_Ru(II)-Ru(in)-Ru(III) trimer [Ru3(Et2dtc)6(DMSO)2](I 3)2, 5, which crystallizes in the triclinic space group P1̄ with a = 14.125(3) Å, b = 20.829(6) Å, c = 13.658(3) Å, a = 97.57(2)°, β= 110.01(2)°, and γ = 71.25(2)° for 2=2. The structure of complex 6 can be viewed as consisting of a {Ru2 III(Et2dtc)4}2+ core and a {RuII(Et2dtc)2(DMSO)2} moiety, which are linked together via the two dithiocarbamate sulfurs of the latter. While the two Ru(III) centers are connected by a Ru-Ru single bond (Ru-Ru = 2.826(2) Å), there is no direct interaction between the Ru(III) and Ru(II) centers. Oxidation of Ru(Et2dtc)2L2 (L = PPh3, t-BuNC) by I2 gave the respective [Ru(Et2dtc)2L2]+ cations. The reaction of cis-Ru(Et2dtc)2(PPh3)2 with excess tosyl azide gave the diamagnetic Ru(IV) tetrazene complex Ru(Et2dtc)2(Ts2N4), 7. Complex 7 crystallizes in the triclinic space group P1̄ with a = 10.380(1) Å, b = 11.322-(1) Å, c = 15.310(1) Å, α = 106.84(2)°, β = 106.87(2)°, and γ = 92.63(2)° for Z = 2. The Ru-S and Ru-Nα distances in 7 are 2.385 and 1.98 A, respectively. The formal potentials of the Ru dithiocarbamate complexes were determined by cyclic voltammetry.
Persistent Identifierhttp://hdl.handle.net/10722/69434
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLeung, WHen_HK
dc.contributor.authorChim, JLCen_HK
dc.contributor.authorHou, Hen_HK
dc.contributor.authorHun, TSMen_HK
dc.contributor.authorWilliams, IDen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:13:37Z-
dc.date.available2010-09-06T06:13:37Z-
dc.date.issued1997en_HK
dc.identifier.citationInorganic Chemistry, 1997, v. 36 n. 20, p. 4432-4437en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69434-
dc.description.abstractThe reaction of Ru(Et2dtc)2(DMSO)2 (Et2dtc = N,N-diethyldithiocarbamate; DMSO = dimethyl sulfoxide) with t-BuNC gave trans-Ru(Et2dtc)2(CN-t-Bu)2, 1. Complex 1 crystallizes in the monoclinic space group P21/n with a = 9.753(2) Å, b = 11.583(2) Å, c = 12.974(2) Å, and β = 91.8(2)° for Z = 2. The crystal structure of 1 shows the trans disposition of the two isocyanides; the mean Ru-S and Ru-C distances are 2.409 and 1.977(2) Å, respectively. Treatment of [Ru(diene)Cl2]n with Na(Et2dtc) afforded Ru(Et2dtc)2(diene) (diene = bicyclo[2.2.1]-hepta-2,5-diene (NBD), 2, 1,5-cyclooctadiene (COD), 3). Complex 2 crystallizes in the triclinic space group P1̄ with a = 7.316(1) Å, b = 10.346(1) Å, c = 15.123(2) Å, a = 103.69(2)°, β= 93.54(2)°, and γ = 100.61(2)° for Z = 2. The mean Ru-S and Ru-C distances in 2 are 2.416 and 2.137 Å, respectively. The reaction of cis-Ru(Et2dtc)2(CO)2 with iodine gave the 2:1 molecular iodine complex cis-Ru(Et2dtc)2(CO)2·1/2I2 4, which crystallizes in the monoclinic space group P21/c with a 7.347(2), b = 22.227(2) Å, c = 12.891(2) Å, and β =95.98 (2)° for Z = 4. The mean Ru-S and Ru-C and the I-I distances in complex 4 are 2.427, 1.903, and 2.745(1) Å, respectively. Treatment of Ru(Et2dtc)2(DMSO)2 with I2 gave the linear_Ru(II)-Ru(in)-Ru(III) trimer [Ru3(Et2dtc)6(DMSO)2](I 3)2, 5, which crystallizes in the triclinic space group P1̄ with a = 14.125(3) Å, b = 20.829(6) Å, c = 13.658(3) Å, a = 97.57(2)°, β= 110.01(2)°, and γ = 71.25(2)° for 2=2. The structure of complex 6 can be viewed as consisting of a {Ru2 III(Et2dtc)4}2+ core and a {RuII(Et2dtc)2(DMSO)2} moiety, which are linked together via the two dithiocarbamate sulfurs of the latter. While the two Ru(III) centers are connected by a Ru-Ru single bond (Ru-Ru = 2.826(2) Å), there is no direct interaction between the Ru(III) and Ru(II) centers. Oxidation of Ru(Et2dtc)2L2 (L = PPh3, t-BuNC) by I2 gave the respective [Ru(Et2dtc)2L2]+ cations. The reaction of cis-Ru(Et2dtc)2(PPh3)2 with excess tosyl azide gave the diamagnetic Ru(IV) tetrazene complex Ru(Et2dtc)2(Ts2N4), 7. Complex 7 crystallizes in the triclinic space group P1̄ with a = 10.380(1) Å, b = 11.322-(1) Å, c = 15.310(1) Å, α = 106.84(2)°, β = 106.87(2)°, and γ = 92.63(2)° for Z = 2. The Ru-S and Ru-Nα distances in 7 are 2.385 and 1.98 A, respectively. The formal potentials of the Ru dithiocarbamate complexes were determined by cyclic voltammetry.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.titleOxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II)en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=36&spage=4432&epage=4437&date=1997&atitle=Oxidation+Reactions+of+Dithiocarbamate+Complexes+of+Ruthenium(II)en_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic970053q-
dc.identifier.pmid11670104-
dc.identifier.scopuseid_2-s2.0-0000492076en_HK
dc.identifier.hkuros31378en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000492076&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume36en_HK
dc.identifier.issue20en_HK
dc.identifier.spage4432en_HK
dc.identifier.epage4437en_HK
dc.identifier.isiWOS:A1997XY36100024-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLeung, WH=7201504510en_HK
dc.identifier.scopusauthoridChim, JLC=6602609380en_HK
dc.identifier.scopusauthoridHou, H=7202320199en_HK
dc.identifier.scopusauthoridHun, TSM=6506894270en_HK
dc.identifier.scopusauthoridWilliams, ID=7201818926en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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