| Abstract: | The Reactivity of Dinuclear Platina‐β‐diketones with Phosphines: Diacetylplatinum(II) Complexes and Mononuclear Platina‐β‐diketones Addition of mono‐ and bidentate phosphines or of AsPh3 to the platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] ( 1 ) followed by the addition of NaOMe at ?70 °C resulted in the formation of diacetyl platinum(II) complexes cis‐[Pt(COMe)2L2] (L = PPh3, 2a ; P(4‐FC6H4)3, 2b ; PPh2(4‐py), 2c ; PMePh2, 2d ; AsPh3, 2d ) and [Pt(COMe)2(L??L)] (L??L = dppe, 3b ; dppp, 3c ), respectively. The analogous reaction with dppm afforded the dinuclear complex cis‐[{Pt(COMe)2}2(μ‐dppm)2] ( 4 ) that reacted in boiling acetone yielding [Pt(COMe)2(dppm)] ( 3a ). The reactions 1 → 2 / 3 were found to proceed via thermally highly unstable cationic mononuclear platina‐β‐diketone intermediates [Pt{(COMe)2H}L2]+ and [Pt{(COMe)2H}(L??L)]+, respectively, that could be isolated as chlorides for L??L = dppe ( 5a ) and dppp ( 5b ). The reversibility of the deprotonation of type 5 complexes with NaOMe yielding type 3 complexes was shown by the protonation of the diacetyl complex 3b with HBF4 yielding the platina‐β‐diketone [Pt{(COMe)2H}(dppe)](BF4) ( 5c ). All compounds were fully characterized by means of NMR and IR spectroscopies, and microanalyses. X‐ray diffraction analysis was performed for the complex cis‐[Pt(COMe)2(PPh3)2]·H2O·CHCl3 ( 2a ·H2O·CHCl3). |
