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Article: Dioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]- (Q = S or Se; R = Ph or Pri)
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TitleDioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]- (Q = S or Se; R = Ph or Pri)
 
AuthorsZhang, QF3
Lau, KK3
Chim, JLC
Wong, TKT2
Wong, WT
Williams, ID
Leung, WH1
 
Issue Date2000
 
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
 
CitationJournal of the Chemical Society Dalton Transactions, 2000, n. 17, p. 3027-3033 [How to Cite?]
DOI: http://dx.doi.org/10.1039/B003798M
 
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.
 
ISSN1472-7773
 
DOIhttp://dx.doi.org/10.1039/B003798M
 
ISI Accession Number IDWOS:000088987800024
 
DC FieldValue
dc.contributor.authorZhang, QF
 
dc.contributor.authorLau, KK
 
dc.contributor.authorChim, JLC
 
dc.contributor.authorWong, TKT
 
dc.contributor.authorWong, WT
 
dc.contributor.authorWilliams, ID
 
dc.contributor.authorLeung, WH
 
dc.date.accessioned2010-09-06T06:11:28Z
 
dc.date.available2010-09-06T06:11:28Z
 
dc.date.issued2000
 
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.identifier.citationJournal of the Chemical Society Dalton Transactions, 2000, n. 17, p. 3027-3033 [How to Cite?]
DOI: http://dx.doi.org/10.1039/B003798M
 
dc.identifier.doihttp://dx.doi.org/10.1039/B003798M
 
dc.identifier.epage3033
 
dc.identifier.hkuros56695
 
dc.identifier.isiWOS:000088987800024
 
dc.identifier.issn1472-7773
 
dc.identifier.issue17
 
dc.identifier.openurl
 
dc.identifier.scopuseid_2-s2.0-0000427171
 
dc.identifier.spage3027
 
dc.identifier.urihttp://hdl.handle.net/10722/69198
 
dc.languageeng
 
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
 
dc.publisher.placeUnited Kingdom
 
dc.relation.ispartofJournal of the Chemical Society Dalton Transactions
 
dc.titleDioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]- (Q = S or Se; R = Ph or Pri)
 
dc.typeArticle
 
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<contributor.author>Wong, TKT</contributor.author>
<contributor.author>Wong, WT</contributor.author>
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<description.abstract>Reactions 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&#8211;3 have been characterised by X-ray crystallography. The Os&#8211;O distances in 1&#8211;3 are 1.739, 1.734 and 1.748 &#197;, 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 &#956;-nitrido OsVIII&#8211;OsVI complex [OsN{N(SPPh2)2}2(NOsO3)], in which the [NOsO3]&#8722; is trans to the terminal nitride ligand. The OsVI&#8211;N, OsVI&#8211;N(Os) and OsVIII&#8211;N distances are 1.617(12), 2.318(11), and 1.719(11) &#197;, respectively; the Os(1)&#8211;N(4)&#8211;Os(2) angle being 159.2(7)&#176;. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][ReO4] or [NBu4n]2[M6O19] gave heterometallic &#956;-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&#8211;Os&#8211;S angle and average Os&#8211;S distance are 96.06(5)&#176; and 2.450 &#197;, 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 &#957;(N2) at 2060 and 2040 cm&#8722;1, respectively.</description.abstract>
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Author Affiliations
  1. The University of Hong Kong
  2. Coordination Chemistry Institute, Nanjing University
  3. Hong Kong University of Science and Technology