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Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds
Department of Chemistry, Zhejiang University, Hangzhou 310028, China.
Department of Chemistry, Zhejiang University, Hangzhou 310028, China.
Department of Chemistry, Advanced Research Institute for Science and Engineering, Waseda University, Okubo 3-4-1, Shinjuku Ku, Tokyo, Japan.
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260-3000, United States.
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2006 (English)In: Inorganic Chemistry, ISSN 0020-1669, Vol. 45, no 11, 4526-4536 p.Article in journal (Refereed) Published
Abstract [en]

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 etructurally 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 (1JPtTl), 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 PtIII. 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 Å, 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 PtIII 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. © 2006 American Chemical Society.

Place, publisher, year, edition, pages
2006. Vol. 45, no 11, 4526-4536 p.
National Category
Engineering and Technology
URN: urn:nbn:se:liu:diva-50219DOI: 10.1021/ic051678oOAI: diva2:271115
Available from: 2009-10-11 Created: 2009-10-11 Last updated: 2011-01-11

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Maliarik, Mikhail
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The Institute of TechnologyDepartment of Physics, Chemistry and Biology
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