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Article: Osmium(VI) nitrido and osmium(IV) phosphoraniminato complexes containing schiff base ligands
Title | Osmium(VI) nitrido and osmium(IV) phosphoraniminato complexes containing schiff base ligands |
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Authors | |
Issue Date | 1999 |
Publisher | American 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? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/70349 |
ISSN | 2023 Impact Factor: 4.3 2023 SCImago Journal Rankings: 0.928 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Wong, TW | en_HK |
dc.contributor.author | Lau, TC | en_HK |
dc.contributor.author | Wong, WT | en_HK |
dc.date.accessioned | 2010-09-06T06:22:02Z | - |
dc.date.available | 2010-09-06T06:22:02Z | - |
dc.date.issued | 1999 | en_HK |
dc.identifier.citation | Inorganic Chemistry, 1999, v. 38 n. 26, p. 6181-6186 | en_HK |
dc.identifier.issn | 0020-1669 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/70349 | - |
dc.description.abstract | A 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.language | eng | en_HK |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_HK |
dc.relation.ispartof | Inorganic Chemistry | en_HK |
dc.title | Osmium(VI) nitrido and osmium(IV) phosphoraniminato complexes containing schiff base ligands | en_HK |
dc.type | Article | en_HK |
dc.identifier.openurl | http://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+ligands | en_HK |
dc.identifier.email | Wong, WT: wtwong@hku.hk | en_HK |
dc.identifier.authority | Wong, WT=rp00811 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1021/ic9814571 | - |
dc.identifier.pmid | 11671330 | - |
dc.identifier.scopus | eid_2-s2.0-14544305707 | en_HK |
dc.identifier.hkuros | 53612 | en_HK |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-14544305707&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 38 | en_HK |
dc.identifier.issue | 26 | en_HK |
dc.identifier.spage | 6181 | en_HK |
dc.identifier.epage | 6186 | en_HK |
dc.identifier.isi | WOS:000084525400036 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Wong, TW=8043722600 | en_HK |
dc.identifier.scopusauthorid | Lau, TC=7102222310 | en_HK |
dc.identifier.scopusauthorid | Wong, WT=7403973084 | en_HK |
dc.identifier.issnl | 0020-1669 | - |