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Article: Reaction of a (salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (salen)ruthenium(IV) sulfilamido species

TitleReaction of a (salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (salen)ruthenium(IV) sulfilamido species
Authors
Issue Date2010
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2010, v. 49 n. 1, p. 73-81 How to Cite?
AbstractThe reaction of [Ru vI(N)(L)(MeOH)](PF 6) [1; L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH 3CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru Iv{N(H)SR}(L)(NCCH 3)](PF 6) (2a, R = tBu; 2b, R = Ph). Metathesis of 2a with NaN 3 in methanol affords [Ru Iv{N(H)S tBu}(L) (N 3)l (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(lll) sulfilamine species, [Ru 111HN(H) 2S tBU}(L)(NCCH 3)](PF 6) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(lll) ammine species [Ru 111 (NH 3)(L)(NCCH 3)[PF 6) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 → 2a → 3 (R = tBu), 1 →2b →* 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4cyclohexadiene, and fluorene by 2a are 51,56, and 11, respectively. © 2009 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/70295
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorMan, WLen_HK
dc.contributor.authorLam, WWYen_HK
dc.contributor.authorKwong, HKen_HK
dc.contributor.authorPeng, SMen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLau, TCen_HK
dc.date.accessioned2010-09-06T06:21:32Z-
dc.date.available2010-09-06T06:21:32Z-
dc.date.issued2010en_HK
dc.identifier.citationInorganic Chemistry, 2010, v. 49 n. 1, p. 73-81en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70295-
dc.description.abstractThe reaction of [Ru vI(N)(L)(MeOH)](PF 6) [1; L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH 3CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru Iv{N(H)SR}(L)(NCCH 3)](PF 6) (2a, R = tBu; 2b, R = Ph). Metathesis of 2a with NaN 3 in methanol affords [Ru Iv{N(H)S tBu}(L) (N 3)l (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(lll) sulfilamine species, [Ru 111HN(H) 2S tBU}(L)(NCCH 3)](PF 6) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(lll) ammine species [Ru 111 (NH 3)(L)(NCCH 3)[PF 6) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 → 2a → 3 (R = tBu), 1 →2b →* 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4cyclohexadiene, and fluorene by 2a are 51,56, and 11, respectively. © 2009 American Chemical Society.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.titleReaction of a (salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (salen)ruthenium(IV) sulfilamido speciesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=49&spage=73&epage=81&date=2010&atitle=Reaction+of+a+(Salen)ruthenium(VI)+Nitrido+Complex+with+Thiols.+C-H+Bond+Activation+by+(Salen)ruthenium(IV)+Sulfilamido+Speciesen_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/ic901374fen_HK
dc.identifier.pmid19954163-
dc.identifier.scopuseid_2-s2.0-73349121643en_HK
dc.identifier.hkuros170191en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-73349121643&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume49en_HK
dc.identifier.issue1en_HK
dc.identifier.spage73en_HK
dc.identifier.epage81en_HK
dc.identifier.isiWOS:000272935800011-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridMan, WL=7005307944en_HK
dc.identifier.scopusauthoridLam, WWY=21733437300en_HK
dc.identifier.scopusauthoridKwong, HK=7003727185en_HK
dc.identifier.scopusauthoridPeng, SM=35464852200en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK

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