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Article: Osmium(VI) nitrido and osmium(IV) phosphoraniminato complexes containing schiff base ligands

TitleOsmium(VI) nitrido and osmium(IV) phosphoraniminato complexes containing schiff base ligands
Authors
Issue Date1999
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1999, v. 38 n. 26, p. 6181-6186 How to Cite?
AbstractA series of osmium(VI) nitrido complexes containing Schiff base ligands, [OsVI(N)(L)Cl] (L = salophen or salen), have been synthesized by reaction of the ligand with [NBun 4][OsVI(N)Cl4] in the presence of 2,6-dimethylpyridine. The ν(Os≡N) for the salophen complexes occur at around 1070 cm-1 and are insensitive to the nature of the substituents present on the Schiff base ligand. The structures of [Os(N)(salophen)(MeOH)]ClO4 and [Os(N)(5,5-Cl2salophen)(MeOH)]ClO4 have been determined by X-ray crystallography, and the Os≡N bond distances are 1.651 and 1.66 Å, respectively. The osmium(VI) nitrido complexes react rapidly with triphenylphosphine to produce the corresponding osmium(IV) phosphoraniminato complexes, [OsIV(NPPh3)(L)Cl]. The osmium(IV) complexes exhibit reversible OsV/IV and OsIV/III couples in cyclic voltammetry. The E1/2 values show linear correlations with the Hammett constants σp of the substituents on the Schiff base ligand. The structure of [OsIV(NPPh3)(salophen)-Cl] has been determined by X-ray crystallography. The rather long Os-N(P) bond length (1.92 A) and acute Os-N-P bond angle (149.6°) suggest that there is no significant multiple-bond character in the Os-N bond. The kinetics of nitrogen atom transfer from a series of 5,5′-disubstituted salophen nitrido complexes to PPh3 have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law was obtained: -d[Os(VI)]/dt = k2[Os(VI)][PPh3]. The reactivities of the complexes were found to follow a Hammett correlation of log(kX/kH) with σp, with a ρ value of 1.9 ± 0.1. The positive ρ value is consistent with a transition state involving electrophilic attack by the nitrido ligand on the phosphorus atom. © 1999 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/70349
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorWong, TWen_HK
dc.contributor.authorLau, TCen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:22:02Z-
dc.date.available2010-09-06T06:22:02Z-
dc.date.issued1999en_HK
dc.identifier.citationInorganic Chemistry, 1999, v. 38 n. 26, p. 6181-6186en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70349-
dc.description.abstractA series of osmium(VI) nitrido complexes containing Schiff base ligands, [OsVI(N)(L)Cl] (L = salophen or salen), have been synthesized by reaction of the ligand with [NBun 4][OsVI(N)Cl4] in the presence of 2,6-dimethylpyridine. The ν(Os≡N) for the salophen complexes occur at around 1070 cm-1 and are insensitive to the nature of the substituents present on the Schiff base ligand. The structures of [Os(N)(salophen)(MeOH)]ClO4 and [Os(N)(5,5-Cl2salophen)(MeOH)]ClO4 have been determined by X-ray crystallography, and the Os≡N bond distances are 1.651 and 1.66 Å, respectively. The osmium(VI) nitrido complexes react rapidly with triphenylphosphine to produce the corresponding osmium(IV) phosphoraniminato complexes, [OsIV(NPPh3)(L)Cl]. The osmium(IV) complexes exhibit reversible OsV/IV and OsIV/III couples in cyclic voltammetry. The E1/2 values show linear correlations with the Hammett constants σp of the substituents on the Schiff base ligand. The structure of [OsIV(NPPh3)(salophen)-Cl] has been determined by X-ray crystallography. The rather long Os-N(P) bond length (1.92 A) and acute Os-N-P bond angle (149.6°) suggest that there is no significant multiple-bond character in the Os-N bond. The kinetics of nitrogen atom transfer from a series of 5,5′-disubstituted salophen nitrido complexes to PPh3 have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law was obtained: -d[Os(VI)]/dt = k2[Os(VI)][PPh3]. The reactivities of the complexes were found to follow a Hammett correlation of log(kX/kH) with σp, with a ρ value of 1.9 ± 0.1. The positive ρ value is consistent with a transition state involving electrophilic attack by the nitrido ligand on the phosphorus atom. © 1999 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.titleOsmium(VI) nitrido and osmium(IV) phosphoraniminato complexes containing schiff base ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=38&spage=6181&epage=6186&date=1999&atitle=Osmium(VI)+nitrido+and+osmium(IV)+phosphoraniminato+complexes+containing+schiff+base+ligandsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic9814571-
dc.identifier.pmid11671330-
dc.identifier.scopuseid_2-s2.0-14544305707en_HK
dc.identifier.hkuros53612en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-14544305707&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume38en_HK
dc.identifier.issue26en_HK
dc.identifier.spage6181en_HK
dc.identifier.epage6186en_HK
dc.identifier.isiWOS:000084525400036-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridWong, TW=8043722600en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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