Zur Reaktivität von alkylthioverbrückten 44‐CVE‐triangularen Platinclustern: Umsetzungen mit bidentaten Phosphanliganden |
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| Authors: | Christian Albrecht Clemens Bruhn Christoph Wagner Dirk Steinborn Prof Dr |
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| Institution: | 1. Halle/Saale, Institut für Chemie der Universit?t;2. Kassel, Institut für Chemie der Universit?t |
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| Abstract: | On the Reactivity of Alkylthio Bridged 44 CVE Triangular Platinum Clusters: Reactions with Bidentate Phosphine Ligands The 44 cve (cluster valence electrons) triangular platinum clusters {Pt(PR3)}3(μ‐SMe)3]Cl (PR3 = PPh3, 2a ; P(4‐FC6H4)3, 2b ; P(n‐Bu)3, 2c ) were found to react with PPh2CH2PPh2 (dppm) in a degradation reaction yielding dinuclear platinum(I) complexes {Pt(PR3)}2(μ‐SMe)(μ‐dppm)]Cl (PR3 = PPh3, 3a ; P(4‐FC6H4)3, 3b ; P(n‐Bu)3; 3e ) and the platinum(II) complex Pt(SMe)2(dppm)] ( 4 ), whereas the addition of PPh2CH2CH2PPh2 (dppe) to cluster 2a afforded a mixture of degradation products, among others the complexes Pt(dppe)2] and Pt(dppe)2]Cl2. On the other hand, the treatment of cluster 2a with PPh2CH2CH2CH2PPh2 (dppp) ended up in the formation of the cationic complex {Pt(dppp)}2(μ‐SMe)2]Cl2 ( 5 ). Furthermore, the terminal PPh3 ligands in complex 3a proved to be subject to substitution by the stronger donating monodentate phosphine ligands PMePh2 and PMe2Ph yielding the analogous complexes {Pt(PR3)}2(μ‐SMe)(μ‐dppm)]Cl (PR3 = PMePh2, 3c ; PMe2Ph, 3d ). NMR investigations on complexes 3 showed an inverse correlation of Tolmans electronic parameter ν with the coupling constants 1J(Pt,P) and 1J(Pt,Pt). All compounds were fully characterized by means of NMR and IR spectroscopy. X‐ray diffraction analyses were performed for the complexes {Pt{P(4‐FC6H4)3}}2(μ‐SMe)(μ‐dppm)]Cl ( 3b ), Pt(SMe)2(dppm)] ( 4 ), and {Pt(dppp)}2(μ‐SMe)2]Cl2 ( 5 ). |
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| Keywords: | Platinum clusters Thio ligands Degradation reactions Crystal structures |
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