On the Reactivity of Platina‐β‐diketones – Synthesis and Characterization of Acylplatinum(II) Complexes

The platina‐β‐diketones [Pt₂{(COR)₂H}₂(μ‐Cl)₂] ( 1 , R = Me a , Et b ) react with phosphines L in a molar ratio of 1 : 4 through cleavage of acetaldehyde to give acylplatinum(II) complexes trans‐[Pt(COR)Cl(L)₂] ( 2 ) (R/L = Me/P(p‐FC₆H₄)₃ a , Me/P(p‐CH₂=CHC₆H₄)Ph₂ b , Me/P(n‐Bu)₃ c , Et/P(p‐MeOC₆H₄)₃ d ). 1 a reacts with Ph₂As(CH₂)₂PPh₂ (dadpe) in a molar ratio of 1 : 2 through cleavage of acetaldehyde yielding [Pt(COMe)Cl(dadpe)] ( 3 a ) (configuration index: SP‐4‐4) and [Pt(COMe)Cl(dadpe)] (configuration index: SP‐4‐2) ( 3 b ) in a ratio of about 9 : 1. All acyl complexes were characterized by ¹H, ¹³C and ³¹P NMR spectroscopy. The molecular structures of 2 a and 3 a were determined by single‐crystal X‐ray diffraction. The geometries at the platinum centers are close to square planar. In both complexes the plane of the acyl ligand is nearly perpendicular to the plane of the complex (88(2)° 2 a , 81.2(5)° 3 a ).