Heterobimetallic Pt(II) Complexes Supported by 1,8‐Naphthyridine Ligands Confirm the Rotation of C ₆ F ₅ Groups about the Pt−C Bond

The ligand 1,8‐naphthyridine (napy) exhibits a rich coordination chemistry arising from the disposition of its two nitrogen atoms. In this work, the mononuclear platinum complex cis‐ [Pt(C 6 F 5 ) 2 (napy) 2 ] was synthesized and used to prepare other platinum complexes such as cis ‐[Pt(C 6 F 5 )Cl(napy) 2 ]. More importantly, its suitability as precursor for the synthesis of other heterobimetallic donor–acceptor complexes of the type Pt → M (M = Ag, Cu) was explored. This way, complexes cis ‐[Pt(C 6 F 5 ) 2 ( μ ‐napy) 2 Ag(OClO 3 )] and cis ‐[Pt(C 6 F 5 ) 2 ( μ ‐napy) 2 Cu(NCMe)][PF 6 ] were prepared, in which two napy ligands bridge both metal atoms. In the rare Pt → Cu donor–acceptor complex, the MeCN ligand was easily substituted by a chlorido ligand, resulting in cis ‐[Pt(C 6 F 5 ) 2 ( μ ‐napy) 2 CuCl] and [{Pt(C 6 F 5 ) 2 ( μ ‐napy) 2 Cu} 2 ( μ ‐Cl)][PF 6 ], depending on the stoichiometry. In all cases, the free rotation of the C 6 F 5 ligands about the Pt−C bonds in solution at room temperature can be stopped at low temperature.