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Spectral and struct...
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Chen, W. Z.Department of Chemistry, Zhejiang University, Hangzhou 310028, China
(författare)
Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds
- Artikel/kapitelEngelska2006
Förlag, utgivningsår, omfång ...
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2006-04-25
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American Chemical Society (ACS),2006
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printrdacarrier
Nummerbeteckningar
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LIBRIS-ID:oai:DiVA.org:kth-15690
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https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-15690URI
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https://doi.org/10.1021/ic051678oDOI
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https://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-50219URI
Kompletterande språkuppgifter
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Språk:engelska
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Sammanfattning på:engelska
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Klassifikation
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Ämneskategori:ref swepub-contenttype
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Ämneskategori:art swepub-publicationtype
Anmärkningar
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QC 20100525
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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.
Ämnesord och genrebeteckningar
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density-functional theory
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spin coupling-constants
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cis-diammineplatinum(iii) dinuclear complex
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nuclear-magnetic-resonance
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axial-ligand
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statistical average
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crystal-structures
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aqueous-solution
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chemical-shifts
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pt interactions
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TECHNOLOGY
Biuppslag (personer, institutioner, konferenser, titlar ...)
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Liu, F. H.Department of Chemistry, Zhejiang University, Hangzhou 310028, China
(författare)
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Matsumoto, K.Department of Chemistry, Advanced Research Institute for Science and Engineering, Waseda University, Okubo 3-4-1, Shinjuku Ku, Tokyo, Japan
(författare)
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Autschbach, J.Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260-3000, United States
(författare)
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Le Guennic, B.Le Guennic, B., Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260-3000, United States
(författare)
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Ziegler, T.Department of Chemistry, University of Calgary, Calgary, Alta. T2N 1N4, Canada
(författare)
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Maliarik, MikhailLinköpings universitet,Tekniska högskolan,Institutionen för fysik, kemi och biologi(Swepub:liu)mikma43
(författare)
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Glaser, JuliusKTH,Oorganisk kemi,Department of Chemistry, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden(Swepub:kth)u13oy1f4
(författare)
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Department of Chemistry, Zhejiang University, Hangzhou 310028, ChinaDepartment of Chemistry, Advanced Research Institute for Science and Engineering, Waseda University, Okubo 3-4-1, Shinjuku Ku, Tokyo, Japan
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Inorganic Chemistry: American Chemical Society (ACS)45:11, s. 4526-45360020-16691520-510X
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