Platinum‐Containing Polyoxometalates: syn‐ and anti‐[PtII2(α‐PW11O39)2]10− and Formation of the Metal–Metal‐Bonded di‐PtIII Derivatives |
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| Authors: | Dr. Zhengguo Lin Dr. Natalya V. Izarova Aleksandar Kondinski Xiaolin Xing Dr. Ali Haider Linyuan Fan Dr. Nina Vankova Prof. Thomas Heine Dr. Bineta Keita Prof. Jie Cao Prof. Changwen Hu Prof. Ulrich Kortz |
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| Affiliation: | 1. Department of Life Sciences and Chemistry, Jacobs University, Bremen, Germany;2. Forschungszentrum Jülich, Peter Grünberg Institute, Jülich, Germany;3. Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Russia;4. Department of Physics and Earth Sciences, Jacobs University, Bremen, Germany;5. Key Laboratory of Cluster Science, Ministry of Education of China, Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry, Beijing Institute of Technology, Beijing, PR China;6. Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universit?t Leipzig, Leipzig, Germany;7. Université Paris-Sud, Laboratoire de Chimie-Physique, Orsay, France;8. http://ukortz.user.jacobs‐university.de/ 0000-0002-5472-3058 Department of Life Sciences and Chemistry, Jacobs University, Bremen, Germany |
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| Abstract: | The first examples of dimeric, di‐PtII‐containing heteropolytungstates are reported. The two isomeric di‐platinum(II)‐containing 22‐tungsto‐2‐phosphates [anti‐PtII2(α‐PW11O39)2]10? ( 1 a ) and [syn‐PtII2(α‐PW11O39)2]10? ( 2 a ) were synthesized in aqueous pH 3.5 medium using one‐pot procedures. Polyanions 1 a and 2 a contain a core comprising two face‐on PtO4 units, with a Pt???Pt distance of 2.9–3 Å. Both polyanions were investigated by single‐crystal XRD, IR, TGA, UV/Vis, 31P NMR, ESI‐MS, CID‐MS/MS, electrochemistry, and DFT. On the basis of DFT and electrochemistry, we demonstrated that the {Pt2II} moiety in 1 a and 2 a can undergo fully reversible two‐electron oxidation to {Pt2III}, accompanied by formation of a single Pt?Pt bond. Hence we have discovered the novel subclass of PtIII‐containing heteropolytungstates. |
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| Keywords: | electrochemistry ESI-mass spectrometry metal– metal bonds platinum polyoxometalates |
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