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Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds
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2006 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 45, no 11, 4526-4536 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2006. Vol. 45, no 11, 4526-4536 p.
Keyword [en]
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
URN: urn:nbn:se:kth:diva-15690DOI: 10.1021/ic051678oISI: 000237690700035ScopusID: 2-s2.0-33745711720OAI: diva2:333732
QC 20100525Available from: 2010-08-05 Created: 2010-08-05Bibliographically approved

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Glaser, Julius
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Inorganic Chemistry
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