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Spectral and struct...
Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds
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- Chen, W. Z. (författare)
- Department of Chemistry, Zhejiang University, Hangzhou 310028, China
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- Liu, F. H. (författare)
- Department of Chemistry, Zhejiang University, Hangzhou 310028, China
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- Matsumoto, K. (författare)
- Department of Chemistry, Advanced Research Institute for Science and Engineering, Waseda University, Okubo 3-4-1, Shinjuku Ku, Tokyo, Japan
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- Autschbach, J. (författare)
- Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260-3000, United States
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- Le Guennic, B. (författare)
- Le Guennic, B., Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260-3000, United States
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- Ziegler, T. (författare)
- Department of Chemistry, University of Calgary, Calgary, Alta. T2N 1N4, Canada
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- Maliarik, Mikhail (författare)
- Linköpings universitet,Tekniska högskolan,Institutionen för fysik, kemi och biologi
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- Glaser, Julius (författare)
- KTH,Oorganisk kemi,Department of Chemistry, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden
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(creator_code:org_t)
- 2006-04-25
- 2006
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 45:11, s. 4526-4536
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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https://urn.kb.se/re...
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Abstract
Ämnesord
Stäng
- The reactions of [Pt(NH3)(2)((NHCOBu)-Bu-t)(2)] and TlX3 (X = NO3-, Cl-, CF3CO2-) yielded dinuclear [{Pt(ONO2)(NH3)(2-)((NHCOBu)-Bu-t)}Tl(ONO2)(2)(MeOH)] (2) and trinuclear complexes [{PtX(RNH2)(2)((NHCOBu)-Bu-t)(2)}(2)Tl](+) [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 Pt-195 and Tl-205 NMR spectra, which exhibit very large one-bond spin-spin coupling constants between the heteronuclei ((1)J(PtTl)), 146.8 and 88.84 kHz for 2 and 3, respectively. Both the X-ray photoelectron spectra and the Pt-195 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.
Nyckelord
- density-functional theory
- spin coupling-constants
- cis-diammineplatinum(iii) dinuclear complex
- nuclear-magnetic-resonance
- axial-ligand
- statistical average
- crystal-structures
- aqueous-solution
- chemical-shifts
- pt interactions
- TECHNOLOGY
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