Oxidative addition of halogens to [Pt(S2N2H)(PR3)2]BF4. X-Ray crystal structures of [Pt(S2N2H)X(PMe2Ph)](X = Br or I) and the monoclinic and triclinic polymorphs of [Pt(S2N2H)Br2(PMe2Ph)2]BF4
Abstract
[Pt(S2N2H)(PMe2Ph)2]BF4(1a) reacts with bromine to give the PtIVtrans-dibromo compound [Pt(S2N2H)Br2(PMe2Ph)2]BF4(2). This rapidly isomerises to the cis isomer (α and β forms) which readily undergoes reductive elimination to give [Pt(S2N2H)Br(PMe2Ph)](3). [Pt(S2N2H)I(PMe2Ph)](4) was obtained by the reaction of (1a) with iodine. Similarly, treatment of [Pt(S2N2H)(PR3)2]BF4(PR3= PMe3 or PPrn3) with bromine leads to [Pt(S2N2H)Br(PR3)]. The α and β forms of (2) together with (3) and (4) have been characterised by X-ray crystallography.