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Article: Chiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA

TitleChiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2005, v. 44 n. 11, p. 3942-3954 How to Cite?
AbstractThe syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cydohexane-diamine (H 2Bu- salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H 2Br-salch) are described. Reactions of [Os VI(Bu-salch) O 2] (1a) and [Os VI(Br-salch)O 2] (1b) with PPh 3, p-X-arylamines (X = NO 2, CN), N 2H 4·H 2O, Ph 2NNH 2, SOCl 2, CF 3CO 2H, Br 2, and I 2 under reducing conditions gave [Os II(Br-salch)(OPPh 3) 2] (2), [Os VI(Br-salch)(p-X-C 6H 4NH) 2] (3), [μ-O{Os IV(Bu-salch)(p-NO 2C 6H 4-NH)} 2] (4), [Os II(Br-salch)(N 2)(H 2O)] (5), [Os IV(Bu-salch)(OH)(Cl)] (6), [Os IV(Bu-salch)(OH) 2] (7), [Os IV(Bu-salch)-Cl 2] (8), [Os IV(Bu-salch)(CF 3CO 2) 2] (9), [Os IV(Bu-salch)Br 2] (10), and [Os IV(Bu-salch) I 2] (11), respectively. X-ray crystal structure determinations of [Os IV(Br-salch)(p-NO 2C 6H 4NH) 2] (3a), [Os IV(Br-salch)(p-CNC 6H 4NH) 2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) Å for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) Å for 6 and 8, Os-O(CF 3CO 2) distances of 2.025(6)-2.041(6) Å for 9, and Os-I distances of 2.6884(6)-2.6970(6) Å for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79% ee) and moderate trans selectivity. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167933
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorZhang, Jen_HK
dc.contributor.authorLiang, JLen_HK
dc.contributor.authorSun, XRen_HK
dc.contributor.authorZhou, HBen_HK
dc.contributor.authorZhu, NYen_HK
dc.contributor.authorZhou, ZYen_HK
dc.contributor.authorChan, PWHen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:13:06Z-
dc.date.available2012-10-08T03:13:06Z-
dc.date.issued2005en_HK
dc.identifier.citationInorganic Chemistry, 2005, v. 44 n. 11, p. 3942-3954en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167933-
dc.description.abstractThe syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cydohexane-diamine (H 2Bu- salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H 2Br-salch) are described. Reactions of [Os VI(Bu-salch) O 2] (1a) and [Os VI(Br-salch)O 2] (1b) with PPh 3, p-X-arylamines (X = NO 2, CN), N 2H 4·H 2O, Ph 2NNH 2, SOCl 2, CF 3CO 2H, Br 2, and I 2 under reducing conditions gave [Os II(Br-salch)(OPPh 3) 2] (2), [Os VI(Br-salch)(p-X-C 6H 4NH) 2] (3), [μ-O{Os IV(Bu-salch)(p-NO 2C 6H 4-NH)} 2] (4), [Os II(Br-salch)(N 2)(H 2O)] (5), [Os IV(Bu-salch)(OH)(Cl)] (6), [Os IV(Bu-salch)(OH) 2] (7), [Os IV(Bu-salch)-Cl 2] (8), [Os IV(Bu-salch)(CF 3CO 2) 2] (9), [Os IV(Bu-salch)Br 2] (10), and [Os IV(Bu-salch) I 2] (11), respectively. X-ray crystal structure determinations of [Os IV(Br-salch)(p-NO 2C 6H 4NH) 2] (3a), [Os IV(Br-salch)(p-CNC 6H 4NH) 2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) Å for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) Å for 6 and 8, Os-O(CF 3CO 2) distances of 2.025(6)-2.041(6) Å for 9, and Os-I distances of 2.6884(6)-2.6970(6) Å for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79% ee) and moderate trans selectivity. © 2005 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleChiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDAen_HK
dc.typeArticleen_HK
dc.identifier.emailZhu, NY: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityZhu, NY=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic0481935en_HK
dc.identifier.pmid15907122-
dc.identifier.scopuseid_2-s2.0-20444482485en_HK
dc.identifier.hkuros107022-
dc.identifier.hkuros15907122-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-20444482485&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume44en_HK
dc.identifier.issue11en_HK
dc.identifier.spage3942en_HK
dc.identifier.epage3954en_HK
dc.identifier.isiWOS:000229381600025-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridZhang, J=16148295400en_HK
dc.identifier.scopusauthoridLiang, JL=7404541484en_HK
dc.identifier.scopusauthoridSun, XR=7405618613en_HK
dc.identifier.scopusauthoridZhou, HB=7404742589en_HK
dc.identifier.scopusauthoridZhu, NY=7201449530en_HK
dc.identifier.scopusauthoridZhou, ZY=7406096262en_HK
dc.identifier.scopusauthoridChan, PWH=13607033800en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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