Chemistry of acetoacetanilide and derivatives with zero-and di-valent platinum and palladium complexes; crystal structure of the four-membered ring palladalactam complex [Pd{CH(COMe)C(O)NPh}(bipy)](bipy = 2,2′-bipyridyl)
摘要:
Reaction of the complexes cis-[MCl2L2] [M = Pd, L2 = 2,2'-bipyridyl (bipy); M = Pt, L = PPh3 or L2 = cycloocta-1,5-diene or Ph2P(CH2)3PPh2] with acetoacetanilide, o- or p-acetoacetanisidide mediated by silver (1) oxide gave, under mild conditions, high yields of the metallalactam complexes [M{CH(COMe)C(O)NR}L2] (R = Ph, C6H4OMe-o or p). The complexes have been fully characterised by multinuclear NMR spectroscopy, fast atom bombardment mass spectrometry, and by a single-crystal X-ray diffraction study carried out on the 2,2'-bipyridyl palladium derivative [Pd{CH(COMe)C(O)NPh}-(bipy)]. The complex contains a slightly puckered palladalactam ring system (fold angle 17.5-degrees). Reaction of acetoacetanilide with the zerovalent platinum complex [Pt(trans-PhCH=CHPh) (PPh3)2] in air gives exclusively the peroxometallacyclic complex [Pt{OOC(Me) [CH2C(O)NHPh]O}(PPh3)2], while reaction with [Pt(PPh3)4] gave a mixture of the peroxometallacycle plus the platinalactam complex [Pt{CH(COMe)C(O)NPh}(PPh3)2].