Acetonyl platinum(II) complexes

Article abstract of DOI:10.1021/om700665n

Me₄N[Pt{CH₂C(O)Me}Cl₂(η²- C₂H₄)] (1), reacts either (1) with neutral ligands to afford cis-Me₄N[Pt{CH₂C(O)Me}Cl₂(L)] (L = CO (2), η²-PhCH=CH₂ (3), η²-PhC=CPh (4), η²-H₂C=C=CMe₂ (5), PPh₃ (6), AsPh₃ (7)), trans- or/and cis-[Pt{CH₂C(O)Me}CIL ₂] (L = PPh₃ (8), AsPh₃ (9), tht (10), XyNC (11), 'BuNC (12), py (17)), [Pt(CH₂C(O)Me)Cl(η²-C ₂H₄)(L)] (L = py (16)), or cIS-[Pt{CH₂C(O)Me} ClL₂] (L₂ = norbornadiene (nbd, 18), 1,5-cyclooctadiene (cod, 19), bis(diphenylphosphino)methane (dppm, 20), 4,4′-di-tert-butyl-2, 2′-bipyridyl (dbbpy, 21)) or (2) with [Tl(acac)] to give [Pt{CH ₂C(O)Me}(O,Oacac)(η²-C₂H₄)] (22) which reacts with neutral ligands to give [Pt{CH₂C(O)Me}(O,O-acac) (L)] (L = CO (23), PPh₃ (24), XyNC (25)). The different behavior of py and stronger π-acceptor ligands, as CO and PR₃ toward 1, has been explained through a DFT study. Reaction of 11trans with 2 equiv of XyNC affords a mixture of trans-[Pt(C(O)NHXy JCl(CNXy)₂] (13) and irans-[Pt{C(NHXy)₂}Cl(CNXy)₂]Cl (14). The first was isolated by recrystallization and the latter by reacting CW-[PtCl2(CNXy)2] with 2 equiv of XyNC. However, cis-[Pt{CH₂C(O)Me}₂(bpy)] reacts with 4 equiv of XyNC to give cis-[Pt(CH₂C(O)Me)₂(CNXy) ₂] (15).