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Article: Synthesis and reactivity of osmium (VI) nitrido complexes containing pyridine-carboxylato ligands

TitleSynthesis and reactivity of osmium (VI) nitrido complexes containing pyridine-carboxylato ligands
Authors
Keywords2-Quinaldinate
Osmium(VI) nitride
Phosphiniminate
Pyridine-2-carboxylate
Thionitrosyl
Issue Date2009
PublisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/ica
Citation
Inorganica Chimica Acta, 2009, v. 362 n. 10, p. 3576-3582 How to Cite?
AbstractA series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)2X (L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH3O (2b)) and [OsVI(N)(L)X3]- (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)2X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh3)(L)2X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)2Br (2c) (L = 2-quinaldinate) with triphenylphosphine have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained: -d[Os(VI)]/dt = k2[Os(VI)][PPh3]. OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N3) to give an osmium(III) dichloro complex, trans-[PPN][OsIII(L)2Cl2] (6). Reaction of OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex OsII(NS)(L)2Cl (7). These complexes have been structurally characterised by X-ray crystallography. © 2009 Elsevier B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/70368
ISSN
2015 Impact Factor: 1.918
2015 SCImago Journal Rankings: 0.584
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council of Hong KongCityU 101505
CityU 2/06C
Funding Information:

The work described in this paper was supported by the Research Grants Council of Hong Kong ( CityU 101505 and CityU 2/06C).

References
Grants

 

DC FieldValueLanguage
dc.contributor.authorLeung, CFen_HK
dc.contributor.authorYiu, DTYen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorPeng, SMen_HK
dc.contributor.authorLau, TCen_HK
dc.date.accessioned2010-09-06T06:22:12Z-
dc.date.available2010-09-06T06:22:12Z-
dc.date.issued2009en_HK
dc.identifier.citationInorganica Chimica Acta, 2009, v. 362 n. 10, p. 3576-3582en_HK
dc.identifier.issn0020-1693en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70368-
dc.description.abstractA series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)2X (L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH3O (2b)) and [OsVI(N)(L)X3]- (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)2X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh3)(L)2X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)2Br (2c) (L = 2-quinaldinate) with triphenylphosphine have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained: -d[Os(VI)]/dt = k2[Os(VI)][PPh3]. OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N3) to give an osmium(III) dichloro complex, trans-[PPN][OsIII(L)2Cl2] (6). Reaction of OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex OsII(NS)(L)2Cl (7). These complexes have been structurally characterised by X-ray crystallography. © 2009 Elsevier B.V. All rights reserved.en_HK
dc.languageengen_HK
dc.publisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/icaen_HK
dc.relation.ispartofInorganica Chimica Actaen_HK
dc.rightsInorganica Chimica Acta. Copyright © Elsevier BV.en_HK
dc.subject2-Quinaldinateen_HK
dc.subjectOsmium(VI) nitrideen_HK
dc.subjectPhosphiniminateen_HK
dc.subjectPyridine-2-carboxylateen_HK
dc.subjectThionitrosylen_HK
dc.titleSynthesis and reactivity of osmium (VI) nitrido complexes containing pyridine-carboxylato ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1693&volume=362&spage=3576&epage=3582&date=2009&atitle=Synthesis+and+Reactivity+of+Osmium+(VI)+Nitrido+Complexes+Containing+Pyridine-carboxylato+Ligandsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.ica.2009.04.002en_HK
dc.identifier.scopuseid_2-s2.0-67349280678en_HK
dc.identifier.hkuros160656en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-67349280678&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume362en_HK
dc.identifier.issue10en_HK
dc.identifier.spage3576en_HK
dc.identifier.epage3582en_HK
dc.identifier.isiWOS:000267944800026-
dc.publisher.placeNetherlandsen_HK
dc.relation.projectGreen Oxidation Chemistry and Technology-
dc.identifier.scopusauthoridLeung, CF=8280665000en_HK
dc.identifier.scopusauthoridYiu, DTY=6603285427en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridPeng, SM=35464852200en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK

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