File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Dioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]- (Q = S or Se; R = Ph or Pri)

TitleDioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]- (Q = S or Se; R = Ph or Pri)
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. 17, p. 3027-3033 How to Cite?
AbstractReactions of trans-K2[OsVIO2(OH)4] with 2 equivalents of HN(QPR2)2 yielded the dioxoosmium(VI) complexes trans-[OsO2{N(QPR2)2}2] (Q = S, R = Ph 1 or Pri2; Q = Se, R = Ph 3). Complexes 1–3 have been characterised by X-ray crystallography. The Os–O distances in 1–3 are 1.739, 1.734 and 1.748 Å, respectively. trans-[OsN{N(QPR2)2}2Cl] (R = Pri, Q = S; R = Ph, Q = Se) were obtained by reactions of [NBu4n][OsNCl4] with K[N(QPR2)2]. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][OsO3N] resulted in formation of a μ-nitrido OsVIII–OsVI complex [OsN{N(SPPh2)2}2(NOsO3)], in which the [NOsO3]− is trans to the terminal nitride ligand. The OsVI–N, OsVI–N(Os) and OsVIII–N distances are 1.617(12), 2.318(11), and 1.719(11) Å, respectively; the Os(1)–N(4)–Os(2) angle being 159.2(7)°. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][ReO4] or [NBu4n]2[M6O19] gave heterometallic μ-oxo complexes trans-[OsN{N(SPPh2)2}2(OReO3)] or trans-[{OsN[N(SPPh2)2]2}2(M6O19)] (M = Mo or W), respectively. Reaction of [NH4]2[OsCl6] with K[N(SPPh2)2] in the presence of PPh3 or treatment of 3 with C6F5SH led to isolation of the osmium(III) homoleptic complexes [Os{N(SPR2)2}3] (R = Pri or Ph). The geometry around Os in the latter is pseudo octahedral, and the average S–Os–S angle and average Os–S distance are 96.06(5)° and 2.450 Å, respectively. Osmium(III) phosphoraniminate complexes [Os(NPMePh2)(PMePh2){N(SPPh2)2}2] and trans-[Os(NPPh3)(PPh3){N(SePPh2)2}2] were prepared by the respective nitridoosmium(VI) complex with PMePh2 or PPh3. Reaction of complex 1 or 2 with hydrazine hydrate afforded air-sensitive osmium(II) dinitrogen species, presumably [Os{N(SPR2)2}2(N2)] (R = Ph or Pri), which exhibit IR ν(N2) at 2060 and 2040 cm−1, respectively.
Persistent Identifierhttp://hdl.handle.net/10722/69198
ISSN
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorZhang, QFen_HK
dc.contributor.authorLau, KKen_HK
dc.contributor.authorChim, JLCen_HK
dc.contributor.authorWong, TKTen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorWilliams, IDen_HK
dc.contributor.authorLeung, WHen_HK
dc.date.accessioned2010-09-06T06:11:28Z-
dc.date.available2010-09-06T06:11:28Z-
dc.date.issued2000en_HK
dc.identifier.citationJournal of the Chemical Society Dalton Transactions, 2000, n. 17, p. 3027-3033en_HK
dc.identifier.issn1472-7773en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69198-
dc.description.abstractReactions of trans-K2[OsVIO2(OH)4] with 2 equivalents of HN(QPR2)2 yielded the dioxoosmium(VI) complexes trans-[OsO2{N(QPR2)2}2] (Q = S, R = Ph 1 or Pri2; Q = Se, R = Ph 3). Complexes 1–3 have been characterised by X-ray crystallography. The Os–O distances in 1–3 are 1.739, 1.734 and 1.748 Å, respectively. trans-[OsN{N(QPR2)2}2Cl] (R = Pri, Q = S; R = Ph, Q = Se) were obtained by reactions of [NBu4n][OsNCl4] with K[N(QPR2)2]. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][OsO3N] resulted in formation of a μ-nitrido OsVIII–OsVI complex [OsN{N(SPPh2)2}2(NOsO3)], in which the [NOsO3]− is trans to the terminal nitride ligand. The OsVI–N, OsVI–N(Os) and OsVIII–N distances are 1.617(12), 2.318(11), and 1.719(11) Å, respectively; the Os(1)–N(4)–Os(2) angle being 159.2(7)°. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][ReO4] or [NBu4n]2[M6O19] gave heterometallic μ-oxo complexes trans-[OsN{N(SPPh2)2}2(OReO3)] or trans-[{OsN[N(SPPh2)2]2}2(M6O19)] (M = Mo or W), respectively. Reaction of [NH4]2[OsCl6] with K[N(SPPh2)2] in the presence of PPh3 or treatment of 3 with C6F5SH led to isolation of the osmium(III) homoleptic complexes [Os{N(SPR2)2}3] (R = Pri or Ph). The geometry around Os in the latter is pseudo octahedral, and the average S–Os–S angle and average Os–S distance are 96.06(5)° and 2.450 Å, respectively. Osmium(III) phosphoraniminate complexes [Os(NPMePh2)(PMePh2){N(SPPh2)2}2] and trans-[Os(NPPh3)(PPh3){N(SePPh2)2}2] were prepared by the respective nitridoosmium(VI) complex with PMePh2 or PPh3. Reaction of complex 1 or 2 with hydrazine hydrate afforded air-sensitive osmium(II) dinitrogen species, presumably [Os{N(SPR2)2}2(N2)] (R = Ph or Pri), which exhibit IR ν(N2) at 2060 and 2040 cm−1, respectively.-
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.titleDioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]- (Q = S or Se; R = Ph or Pri)en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=3027&epage=3033&date=2000&atitle=Dioxo-+and+nitrido-osmium+complexes+with+imidodiphosphinochalcogenido+ligands+[N(QPR2)2]-+(Q+=+S+or+Se;++R+=+Ph+or+Pri)en_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1039/B003798M-
dc.identifier.scopuseid_2-s2.0-0000427171-
dc.identifier.hkuros56695en_HK
dc.identifier.issue17-
dc.identifier.spage3027-
dc.identifier.epage3033-
dc.identifier.isiWOS:000088987800024-
dc.publisher.placeUnited Kingdom-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats