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- PMID: 12132910
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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)
Title | 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) |
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Authors | |
Issue Date | 2002 |
Publisher | American 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? |
Abstract | Structural, 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 Identifier | http://hdl.handle.net/10722/167729 |
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 | Xia, BH | en_US |
dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Phillips, DL | en_US |
dc.contributor.author | Leung, KH | en_US |
dc.contributor.author | Cheung, KK | en_US |
dc.date.accessioned | 2012-10-08T03:10:33Z | - |
dc.date.available | 2012-10-08T03:10:33Z | - |
dc.date.issued | 2002 | en_US |
dc.identifier.citation | Inorganic Chemistry, 2002, v. 41 n. 15, p. 3866-3875 | en_US |
dc.identifier.issn | 0020-1669 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167729 | - |
dc.description.abstract | Structural, 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_US |
dc.relation.ispartof | Inorganic Chemistry | en_US |
dc.title | 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) | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.email | Phillips, DL:phillips@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.identifier.authority | Phillips, DL=rp00770 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ic020077j | en_US |
dc.identifier.pmid | 12132910 | - |
dc.identifier.scopus | eid_2-s2.0-0036074974 | en_US |
dc.identifier.hkuros | 76363 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0036074974&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 41 | en_US |
dc.identifier.issue | 15 | en_US |
dc.identifier.spage | 3866 | en_US |
dc.identifier.epage | 3875 | en_US |
dc.identifier.isi | WOS:000176973400010 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Xia, BH=7102762241 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_US |
dc.identifier.scopusauthorid | Leung, KH=7401860609 | en_US |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_US |
dc.identifier.issnl | 0020-1669 | - |