THIADIAZATRIMETHYLENEMETHANE AND N,N',P-TRIPHENYLPHOSPHONOTHIOIC DIAMIDE COMPLEXES OF PLATINUM(II)

Reaction of N,N'-diphenylthiourea with cis-[PtCl2L2] [L = PPh3, PMePh2, PMe2Ph, PEt2Ph, PPh2(NEt2) or L2 = Ph2PCH2CH2PPh2 (dppe) in the presence of silver(I) oxide gives the thiadiazatrimethylenemethane complexes [activated Pt{SC(=NPh)NPh}L2] an X-ray study on [activated Pt{SC(= NPh)NPh}(PPh3)2] establishing the presence of a flat activated Pt-S-C-N ring. Related activated Pt-S-P-N ring complexes which contain a reactive nucleophilic P = NPh group are formed upon treatment of PhNHP(S) (Ph)NHPh with cis-[PtCl2L2] [L = PPh3, L2 = dppe, Ph2P(CH2)3PPh2 or Ph2P(CH2)4PPh2] and potassium hydroxide. Treatment of [activated Pt{SP(= NPh)(Ph)NPh}L2] with Mel afforded an aminophosphonium salt, whilst with substrates containing either C = O or C = S functionalities new complexes of the type [activated [Pt{SPO(O)(Ph)NPh}L2] or [Pt{SP(S)(Ph)S}L2] were formed respectively.