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Article: Synthesis and reactivity of nitrido-rhenium and -osmium complexes with an oxygen tripod ligand

TitleSynthesis and reactivity of nitrido-rhenium and -osmium complexes with an oxygen tripod ligand
Authors
Issue Date2000
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society, Dalton Transactions, 2000 n. 1, p. 51-56 How to Cite?
AbstractInteraction of [ReNCl3(PPh3)2] or [ReOCl2(PPh3)3] with NaLOEt (LOEt = [Co(η5-C5H5){PO(OEt)2} 3]) afforded [ReLOEtN(PPh3)Cl] 1 and [ReLOEtOCl2] 2, respectively. Reaction of I with AgBF4 gave the nitridorhenium(vi) complex [ReLOEtN(PPh3)Cl]BF4 1·BF4, which has a μeff of 1.8 μB. Treatment of I with MeOSO2CF3, PhCH2Br or [Ph3C]BF4 afforded the respective organoimido species [ReLOEt(NMe)(PPh3)Cl][CF3SO3] 3, [ReLOEt(NCH2Ph)-(PPh3)Cl]Br 4, and [ReLOEt(NCPh3)(PPh3)Cl] 5. Reaction of 1 with [Au(PPh3)(CF3SO3)], [Ru(Et2dtc)(PPh3)2-(CO)(CF3SO 3)], or [ReMeO3] yielded the bimetallic nitrido complexes [Au(PPh3){NReLOEt(PPh3)Cl}j[CF 3SO3] 6, [Ru(Et2dtc)(PPh3)(H2O)(CO){NReL OEt(PPh3)Cl}][CF3SO3] 7 or [ReMeO3{NReLOEt(PPh3)Cl}] 8, respectively. Treatment of [NBu4 n][OsNCl4] with NaLOEt gave [OsLOEtNCl2]J 9. The average Os-O, Os-Cl and Os-N distances in 9 are 2.066, 2.289 and 2.58(1) Å, respectively. Reaction of 9 with PPh3 afforded the osmium(iv) phosphoran iminate species [OsLOEt(NPPh3)Cl2] 10, which has aμeff of 2.0 μB. The average Os-O, Os-Cl and Os-N distances in 10 are 2.099, 2.342, 1.893(5) Å, respectively, the Os-N-P angle being 137.5(3)°. The formal potentials of the LOEt-Re and -Os complexes have been determined by cyclic voltammetry. On the basis of the ReVI-ReV formal potential, the π-donor strength was found to decrease in the order N3- > [NAu(PPh3)]2- > NMe2-. © The Royal Society of Chemistry 2000.
Persistent Identifierhttp://hdl.handle.net/10722/68903
ISSN
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLeung, WHen_HK
dc.contributor.authorChan, EYYen_HK
dc.contributor.authorLai, TCYen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:08:46Z-
dc.date.available2010-09-06T06:08:46Z-
dc.date.issued2000en_HK
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 2000 n. 1, p. 51-56en_HK
dc.identifier.issn1470-479Xen_HK
dc.identifier.urihttp://hdl.handle.net/10722/68903-
dc.description.abstractInteraction of [ReNCl3(PPh3)2] or [ReOCl2(PPh3)3] with NaLOEt (LOEt = [Co(η5-C5H5){PO(OEt)2} 3]) afforded [ReLOEtN(PPh3)Cl] 1 and [ReLOEtOCl2] 2, respectively. Reaction of I with AgBF4 gave the nitridorhenium(vi) complex [ReLOEtN(PPh3)Cl]BF4 1·BF4, which has a μeff of 1.8 μB. Treatment of I with MeOSO2CF3, PhCH2Br or [Ph3C]BF4 afforded the respective organoimido species [ReLOEt(NMe)(PPh3)Cl][CF3SO3] 3, [ReLOEt(NCH2Ph)-(PPh3)Cl]Br 4, and [ReLOEt(NCPh3)(PPh3)Cl] 5. Reaction of 1 with [Au(PPh3)(CF3SO3)], [Ru(Et2dtc)(PPh3)2-(CO)(CF3SO 3)], or [ReMeO3] yielded the bimetallic nitrido complexes [Au(PPh3){NReLOEt(PPh3)Cl}j[CF 3SO3] 6, [Ru(Et2dtc)(PPh3)(H2O)(CO){NReL OEt(PPh3)Cl}][CF3SO3] 7 or [ReMeO3{NReLOEt(PPh3)Cl}] 8, respectively. Treatment of [NBu4 n][OsNCl4] with NaLOEt gave [OsLOEtNCl2]J 9. The average Os-O, Os-Cl and Os-N distances in 9 are 2.066, 2.289 and 2.58(1) Å, respectively. Reaction of 9 with PPh3 afforded the osmium(iv) phosphoran iminate species [OsLOEt(NPPh3)Cl2] 10, which has aμeff of 2.0 μB. The average Os-O, Os-Cl and Os-N distances in 10 are 2.099, 2.342, 1.893(5) Å, respectively, the Os-N-P angle being 137.5(3)°. The formal potentials of the LOEt-Re and -Os complexes have been determined by cyclic voltammetry. On the basis of the ReVI-ReV formal potential, the π-donor strength was found to decrease in the order N3- > [NAu(PPh3)]2- > NMe2-. © The Royal Society of Chemistry 2000.en_HK
dc.languageengen_HK
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofJournal of the Chemical Society, Dalton Transactionsen_HK
dc.titleSynthesis and reactivity of nitrido-rhenium and -osmium complexes with an oxygen tripod liganden_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=51&epage=56&date=2000&atitle=Synthesis+and+reactivity+of+nitrido-rhenium+and+-osmium+complexes+with+an+oxygen+tripod+liganden_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/A906618G-
dc.identifier.scopuseid_2-s2.0-0008323703en_HK
dc.identifier.hkuros53809en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0008323703&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue1en_HK
dc.identifier.spage51en_HK
dc.identifier.epage56en_HK
dc.identifier.isiWOS:000084955700009-
dc.identifier.scopusauthoridLeung, WH=7201504510en_HK
dc.identifier.scopusauthoridChan, EYY=7401994108en_HK
dc.identifier.scopusauthoridLai, TCY=24470680800en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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