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

✍ Scribed by Dirk Steinborn; Tobias Hoffmann; Michael Gerisch; Clemens Bruhn; Harry Schmidt; Karsten Nordhoff; Julian A. Davies; Kristin Kirschbaum; Ingo Jolk

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: German
• Weight: 139 KB
• Volume: 626
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(200003)626:3<661::aid-zaac661>3.0.co;2-4

✦ Synopsis

The platina-b-diketones [Pt 2 {(COR) 2 H} 2 (l-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-FC 6 H 4 ) 3 a, Me/P(p-CH 2 =CHC 6 H 4 )Ph 2 b, Me/P(n-Bu) 3 c, Et/P(p-MeOC 6 H 4 ) 3 d). 1 a reacts with Ph 2 As(CH 2 ) 2 PPh 2 (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 1 H, 13

C and 31 P 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).