MONONUCLEAR PT(II) AND PD(II) 1,4-DITHIOLATO COMPLEXES - CRYSTAL-STRUCTURES OF [PT((-)DIOS)(PPH3)(2)] AND [PD(S(CH2)(4)S)(PH2P(CH2)(3)PPH2)] - APPLICATION IN STYRENE HYDROFORMYLATION

Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P =(PPh3)(2), Ph2P(CH2)(3)PPh2, Phd(2)P(CH2)(4)PPh2; 1,4-dithiols = HS(CH2)(4)SH, (-)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-L-threitol) , BINASH(2) (1,1'-dinaphthalene-2,2'-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P = Ph2P(CH2)(3)PPh2, Ph2P(CH2)(4)PPh2; dithiolato = S-(CH2)(4)S-, (-)-DIOS) were prepared by the same method. The structure of [Pt((-)DIOS)(PPh3)(2)] and [Pd(S( CH2)(4)S)(Ph2P(CH2)(3)PPh2)] complexes was determined by X-ray diffrac tion methods. Pt-dithiolato-SnCl2 systems are active in the hydroformy lation of styrene. At 100 atm and 125 degrees C [Pt(dithiolate)(P-P)]/ SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%.