Beschreibung:
<jats:title>Abstract</jats:title><jats:p><jats:bold>On the Reactivity of Alkylthio Bridged 44 CVE Triangular Platinum Clusters: Reactions with Bidentate Phosphine Ligands</jats:bold></jats:p><jats:p>The 44 cve (cluster valence electrons) triangular platinum clusters [{Pt(PR<jats:sub>3</jats:sub>)}<jats:sub>3</jats:sub>(μ‐SMe)<jats:sub>3</jats:sub>]Cl (PR<jats:sub>3</jats:sub> = PPh<jats:sub>3</jats:sub>, <jats:bold>2a</jats:bold>; P(4‐FC<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>, <jats:bold>2b</jats:bold>; P(<jats:italic>n</jats:italic>‐Bu)<jats:sub>3</jats:sub>, <jats:bold>2c</jats:bold>) were found to react with PPh<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>PPh<jats:sub>2</jats:sub> (dppm) in a degradation reaction yielding dinuclear platinum(I) complexes [{Pt(PR<jats:sub>3</jats:sub>)}<jats:sub>2</jats:sub>(μ‐SMe)(μ‐dppm)]Cl (PR<jats:sub>3</jats:sub> = PPh<jats:sub>3</jats:sub>, <jats:bold>3a</jats:bold>; P(4‐FC<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>, <jats:bold>3b</jats:bold>; P(<jats:italic>n</jats:italic>‐Bu)<jats:sub>3</jats:sub>; <jats:bold>3e</jats:bold>) and the platinum(II) complex [Pt(SMe)<jats:sub>2</jats:sub>(dppm)] (<jats:bold>4</jats:bold>), whereas the addition of PPh<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>PPh<jats:sub>2</jats:sub> (dppe) to cluster <jats:bold>2a</jats:bold> afforded a mixture of degradation products, among others the complexes [Pt(dppe)<jats:sub>2</jats:sub>] and [Pt(dppe)<jats:sub>2</jats:sub>]Cl<jats:sub>2</jats:sub>. On the other hand, the treatment of cluster <jats:bold>2a</jats:bold> with PPh<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>PPh<jats:sub>2</jats:sub> (dppp) ended up in the formation of the cationic complex [{Pt(dppp)}<jats:sub>2</jats:sub>(μ‐SMe)<jats:sub>2</jats:sub>]Cl<jats:sub>2</jats:sub> (<jats:bold>5</jats:bold>). Furthermore, the terminal PPh<jats:sub>3</jats:sub> ligands in complex <jats:bold>3a</jats:bold> proved to be subject to substitution by the stronger donating monodentate phosphine ligands PMePh<jats:sub>2</jats:sub> and PMe<jats:sub>2</jats:sub>Ph yielding the analogous complexes [{Pt(PR<jats:sub>3</jats:sub>)}<jats:sub>2</jats:sub>(μ‐SMe)(μ‐dppm)]Cl (PR<jats:sub>3</jats:sub> = PMePh<jats:sub>2</jats:sub>, <jats:bold>3c</jats:bold>; PMe<jats:sub>2</jats:sub>Ph, <jats:bold>3d</jats:bold>). NMR investigations on complexes <jats:bold>3</jats:bold> showed an inverse correlation of <jats:italic>Tolmans</jats:italic> electronic parameter ν with the coupling constants <jats:sup>1</jats:sup><jats:italic>J</jats:italic>(Pt,P) and <jats:sup>1</jats:sup><jats:italic>J</jats:italic>(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‐FC<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>}}<jats:sub>2</jats:sub>(μ‐SMe)(μ‐dppm)]Cl (<jats:bold>3b</jats:bold>), [Pt(SMe)<jats:sub>2</jats:sub>(dppm)] (<jats:bold>4</jats:bold>), and [{Pt(dppp)}<jats:sub>2</jats:sub>(μ‐SMe)<jats:sub>2</jats:sub>]Cl<jats:sub>2</jats:sub> (<jats:bold>5</jats:bold>).</jats:p>