On the Reactivity of the Platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)

Abstract

AbstractThe reaction of the electronically unsaturated platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] (1) with Ph2PCH2CH2CH2SPh (2) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP‐4‐3)‐[Pt(COMe)Cl(Ph2PCH2CH2CH2SPh‐κP,κS)] (4) having the γ‐phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP‐4‐3)‐[PtMeCl(Ph2PCH2CH2CH2SPh‐κP,κS)] (6). However, the reaction of 1 with the analogous γ‐diphenylphosphinofunctionalized propyl phenyl sulfone Ph2PCH2CH2CH2SO2Ph (3) affords the acetyl(chlorido) platinum(II) complex (SP‐4‐4)‐[Pt(COMe)Cl(Ph2PCH2CH2CH2SO2Ph‐κP)2] (5). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP‐4‐4)‐[PtMeCl(Ph2PCH2CH2CH2SO2Ph‐κP)2] (8) whereas in presence of 1 the formation of the carbonyl complex (SP‐4‐3)‐[PtMeCl(CO)(Ph2PCH2CH2CH2SO2Ph‐κP)] (7) is observed. Addition of Ag[BF4] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP‐4‐1)‐[PtMe(CO)(Ph2PCH2CH2CH2SO2Ph‐κP)2][BF4] (9). All complexes were characterized by microanalysis and NMR spectroscopy (1H, 13C, 31P) and complexes 4 and 6 additionally by single‐crystal X‐ray diffraction analyses.