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Article: Metal-metal interactions in dinuclear d 8 metal cyanide complexes supported by phosphine ligands. Spectroscopic properties and ab initio calculations of [M 2(μ-diphosphine) 2(CN) 4] and trans-[M(phosphine) 2(CN) 2] (M = Pt, Ni)

TitleMetal-metal interactions in dinuclear d 8 metal cyanide complexes supported by phosphine ligands. Spectroscopic properties and ab initio calculations of [M 2(μ-diphosphine) 2(CN) 4] and trans-[M(phosphine) 2(CN) 2] (M = Pt, Ni)
Authors
Issue Date2002
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2002, v. 41 n. 15, p. 3866-3875 How to Cite?
AbstractStructural, spectroscopic properties on the dinuclear [M 2(dcpm) 2(CN) 4] (M = Pt, 1a; Ni, 2a, dcpm = bis(dicyclohexylphosphino)methane) and [M 2(dmpm) 2(CN) 4] (M = Pt, 1b; Ni, 2b, dmpm = bis(dimethylphosphino)-methane) and the mononuclear trans-[M(PCy 3) 2(CN) 2] (M = Pt, 3; Ni, 4, PCy 3 = tricyclohexylphosphine) and theoretical investigations on the corresponding model compounds are described. X-ray structural analyses reveal Pt···Pt and Ni···Ni distances of 3.0565(4)/3.189(1) Å and 2.957(1)/3.209(8) Å for 1a/1b and 2a/2b, respectively. The UV-vis absorption bands at 337 nm (ε 2.41 × 10 4 dm 3 mol -1 cm -1) for 1a and 328 nm (ε 2.43 × 10 4 dm 3 mol -1 cm -1) for 1b in CH 2Cl 2 are assigned to 1(5d σ* → 6p σ) electronic transitions originating from Pt(II)-Pt(II) interactions. Resonance Raman spectroscopy of 1a, in which all the Raman intensity appears in the Pt-Pt stretch fundamental (93 cm -1) and overtone bands, verifies this metal-metal interaction. Complexes 1a and 1b exhibit photoluminescence in the solid state and solution. For the dinuclear nickel(II) complexes 2a and 2b, neither spectroscopic data nor theoretical calculation suggests the presence of Ni(II)-Ni(II) interactions. The intense absorption bands at λ > 320 nm in the UV-vis spectra of 2a and 2b are tentatively assigned to d → d transitions.
Persistent Identifierhttp://hdl.handle.net/10722/167729
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorXia, BHen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorLeung, KHen_US
dc.contributor.authorCheung, KKen_US
dc.date.accessioned2012-10-08T03:10:33Z-
dc.date.available2012-10-08T03:10:33Z-
dc.date.issued2002en_US
dc.identifier.citationInorganic Chemistry, 2002, v. 41 n. 15, p. 3866-3875en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167729-
dc.description.abstractStructural, spectroscopic properties on the dinuclear [M 2(dcpm) 2(CN) 4] (M = Pt, 1a; Ni, 2a, dcpm = bis(dicyclohexylphosphino)methane) and [M 2(dmpm) 2(CN) 4] (M = Pt, 1b; Ni, 2b, dmpm = bis(dimethylphosphino)-methane) and the mononuclear trans-[M(PCy 3) 2(CN) 2] (M = Pt, 3; Ni, 4, PCy 3 = tricyclohexylphosphine) and theoretical investigations on the corresponding model compounds are described. X-ray structural analyses reveal Pt···Pt and Ni···Ni distances of 3.0565(4)/3.189(1) Å and 2.957(1)/3.209(8) Å for 1a/1b and 2a/2b, respectively. The UV-vis absorption bands at 337 nm (ε 2.41 × 10 4 dm 3 mol -1 cm -1) for 1a and 328 nm (ε 2.43 × 10 4 dm 3 mol -1 cm -1) for 1b in CH 2Cl 2 are assigned to 1(5d σ* → 6p σ) electronic transitions originating from Pt(II)-Pt(II) interactions. Resonance Raman spectroscopy of 1a, in which all the Raman intensity appears in the Pt-Pt stretch fundamental (93 cm -1) and overtone bands, verifies this metal-metal interaction. Complexes 1a and 1b exhibit photoluminescence in the solid state and solution. For the dinuclear nickel(II) complexes 2a and 2b, neither spectroscopic data nor theoretical calculation suggests the presence of Ni(II)-Ni(II) interactions. The intense absorption bands at λ > 320 nm in the UV-vis spectra of 2a and 2b are tentatively assigned to d → d transitions.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleMetal-metal interactions in dinuclear d 8 metal cyanide complexes supported by phosphine ligands. Spectroscopic properties and ab initio calculations of [M 2(μ-diphosphine) 2(CN) 4] and trans-[M(phosphine) 2(CN) 2] (M = Pt, Ni)en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic020077jen_US
dc.identifier.pmid12132910-
dc.identifier.scopuseid_2-s2.0-0036074974en_US
dc.identifier.hkuros76363-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0036074974&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume41en_US
dc.identifier.issue15en_US
dc.identifier.spage3866en_US
dc.identifier.epage3875en_US
dc.identifier.isiWOS:000176973400010-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridXia, BH=7102762241en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridLeung, KH=7401860609en_US
dc.identifier.scopusauthoridCheung, KK=7402406613en_US

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