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Article: Formation of μ-dinitrogen (salen)osmium complexes via ligand-induced N⋯N coupling of (salen)osmium(vi) nitrides

TitleFormation of μ-dinitrogen (salen)osmium complexes via ligand-induced N⋯N coupling of (salen)osmium(vi) nitrides
Authors
KeywordsOsmium
Ligands
Mineralogy
Nitrides
X ray crystallography
Issue Date2010
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Dalton Transactions, 2010, v. 39 n. 46, p. 11163-11170 How to Cite?
AbstractTreatment of [N nBu 4][Os VI(N)Cl 4] with a stoichiometric amount of H 2L (L = N,N′-bis(salicylidene)-o-cyclohexylenediamine dianion) in the presence of PF 6 - or ClO 4 - in MeOH affords [Os VI(N)(L)(OH 2)](PF 6) 1a and [Os VI(N)(L)(CH 3OH)](ClO 4) 1b, respectively. The structure of 1b has been determined by X-ray crystallography and the OsN bond distance is 1.627(3) Å. In the presence of a N-donor heterocyclic ligand in CH 3CN, 1a reacts at room temperature to afford the mixed-valence μ-N 2 (salen)osmium species [(X)(L)Os III-NN-Os II(L)(X)](PF 6), 2-14 (X = py 2; 4-Mepy 3; 4- tBupy 4; pz 5; 3-Mepz 6; 3,5-Me 2pz 7; Im 8; 1-MeIm 9; 2-MeIm 10; 4-MeIm 11; 1,2-Me 2Im 12; 2-Meozl 13; 4-MeTz 14). These complexes are formed by ligand-induced N⋯N coupling of two [Os VIN] + to give initially [Os III-N 2-Os III] 2+, which is then reduced to give the more stable mixed-valence species [Os III-N 2-Os II] +. Cyclic voltammograms (CVs) of 2-14 show two reversible couples, attributed to Os III,III/Os III,II and Os III,II/Os II,II. The large comproportionation constants (K com) of (5.36-82.3) × 10 13 indicate charge delocalization in these complexes. The structures of 3 and 14 have been determined by X-ray crystallography, the salen ligands are in uncommon cis-β configuration. Oxidations of 4 and 14 by [Cp 2Fe](PF 6) afford the symmetrical species [(X)(L)Os III-NN-Os III(L)(X)](PF 6) 2 (X = 4- tBupy 15; 4-MeTz 16). These are the first stable μ-N 2 diosmium(iii,iii) complexes that have been characterized by X-ray crystallography. © 2010 The Royal Society of Chemistry.
Persistent Identifierhttp://hdl.handle.net/10722/139001
ISSN
2015 Impact Factor: 4.177
2015 SCImago Journal Rankings: 1.404
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council of Hong Kong Special Administrative RegionCityU 101506
Funding Information:

The work described in this paper was financially supported by the Research Grants Council of Hong Kong Special Administrative Region (CityU 101506).

References

 

DC FieldValueLanguage
dc.contributor.authorMan, WLen_HK
dc.contributor.authorChen, Gen_HK
dc.contributor.authorYiu, SMen_HK
dc.contributor.authorShek, Len_HK
dc.contributor.authorWong, WYen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLau, TCen_HK
dc.date.accessioned2011-09-23T05:43:57Z-
dc.date.available2011-09-23T05:43:57Z-
dc.date.issued2010en_HK
dc.identifier.citationDalton Transactions, 2010, v. 39 n. 46, p. 11163-11170en_HK
dc.identifier.issn1477-9226en_HK
dc.identifier.urihttp://hdl.handle.net/10722/139001-
dc.description.abstractTreatment of [N nBu 4][Os VI(N)Cl 4] with a stoichiometric amount of H 2L (L = N,N′-bis(salicylidene)-o-cyclohexylenediamine dianion) in the presence of PF 6 - or ClO 4 - in MeOH affords [Os VI(N)(L)(OH 2)](PF 6) 1a and [Os VI(N)(L)(CH 3OH)](ClO 4) 1b, respectively. The structure of 1b has been determined by X-ray crystallography and the OsN bond distance is 1.627(3) Å. In the presence of a N-donor heterocyclic ligand in CH 3CN, 1a reacts at room temperature to afford the mixed-valence μ-N 2 (salen)osmium species [(X)(L)Os III-NN-Os II(L)(X)](PF 6), 2-14 (X = py 2; 4-Mepy 3; 4- tBupy 4; pz 5; 3-Mepz 6; 3,5-Me 2pz 7; Im 8; 1-MeIm 9; 2-MeIm 10; 4-MeIm 11; 1,2-Me 2Im 12; 2-Meozl 13; 4-MeTz 14). These complexes are formed by ligand-induced N⋯N coupling of two [Os VIN] + to give initially [Os III-N 2-Os III] 2+, which is then reduced to give the more stable mixed-valence species [Os III-N 2-Os II] +. Cyclic voltammograms (CVs) of 2-14 show two reversible couples, attributed to Os III,III/Os III,II and Os III,II/Os II,II. The large comproportionation constants (K com) of (5.36-82.3) × 10 13 indicate charge delocalization in these complexes. The structures of 3 and 14 have been determined by X-ray crystallography, the salen ligands are in uncommon cis-β configuration. Oxidations of 4 and 14 by [Cp 2Fe](PF 6) afford the symmetrical species [(X)(L)Os III-NN-Os III(L)(X)](PF 6) 2 (X = 4- tBupy 15; 4-MeTz 16). These are the first stable μ-N 2 diosmium(iii,iii) complexes that have been characterized by X-ray crystallography. © 2010 The Royal Society of Chemistry.en_HK
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofDalton Transactionsen_HK
dc.subjectOsmium-
dc.subjectLigands-
dc.subjectMineralogy-
dc.subjectNitrides-
dc.subjectX ray crystallography-
dc.titleFormation of μ-dinitrogen (salen)osmium complexes via ligand-induced N⋯N coupling of (salen)osmium(vi) nitridesen_HK
dc.typeArticleen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/c0dt00481ben_HK
dc.identifier.pmid20963250-
dc.identifier.scopuseid_2-s2.0-78649306459en_HK
dc.identifier.hkuros195792en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-78649306459&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume39en_HK
dc.identifier.issue46en_HK
dc.identifier.spage11163en_HK
dc.identifier.epage11170en_HK
dc.identifier.isiWOS:000284314800008-
dc.publisher.placeUnited Kingdomen_HK
dc.identifier.scopusauthoridMan, WL=7005307944en_HK
dc.identifier.scopusauthoridChen, G=36664295500en_HK
dc.identifier.scopusauthoridYiu, SM=43462142100en_HK
dc.identifier.scopusauthoridShek, L=35741917300en_HK
dc.identifier.scopusauthoridWong, WY=7403972153en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK

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