Source:http://linkedlifedata.com/resource/pubmed/id/16711703
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| Predicate | Object |
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| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
11
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| pubmed:dateCreated |
2006-5-22
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| pubmed:abstractText |
The reactions of [Pt(NH3)2(NHCOtBu)2] and TlX3 (X = NO3-, Cl-, CF3CO2-) yielded dinuclear [{Pt(ONO2)(NH3)2(NHCOtBu)}Tl(ONO2)2(MeOH)] (2) and trinuclear complexes [{PtX(RNH2)2(NHCOtBu)2}2Tl]+ [X = NO3- (3), Cl- (5), CF3CO2- (6)], which were spectroscopically and structurally characterized. Strong Pt-Tl interaction in the complexes in solutions was indicated by both 195Pt and 205Tl NMR spectra, which exhibit very large one-bond spin-spin coupling constants between the heteronuclei (1J(PtTl)), 146.8 and 88.84 kHz for 2 and 3, respectively. Both the X-ray photoelectron spectra and the 195Pt chemical shifts reveal that the complexes have Pt centers whose oxidation states are close to that of Pt(III). Characterization of these complexes by X-ray diffraction analysis confirms that the Pt and Tl atoms are held together by very short Pt-Tl bonds and are supported by the bridging amidate ligands. The Pt-Tl bonds are shorter than 2.6 Angstrom, indicating a strong metal-metal attraction between these two metals. Compound 2 was found to activate the C-H bond of acetone to yield a platinum(IV) acetonate complex. This reactivity corresponds to the property of Pt(III) complexes. Density functional theory calculations were able to reproduce the large magnitude of the metal-metal spin-spin coupling constants. The couplings are sensitive to the computational model because of a delicate balance of metal 6s contributions in the frontier orbitals. The computational analysis reveals the role of the axial ligands in the magnitude of the coupling constants.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
May
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| pubmed:issn |
0020-1669
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
29
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| pubmed:volume |
45
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
4526-36
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| pubmed:year |
2006
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| pubmed:articleTitle |
Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds.
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| pubmed:affiliation |
Department of Chemistry, Zhejiang University, Hangzhou 310028, China. chenwzz@zju.edu.cn
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| pubmed:publicationType |
Journal Article
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