Diastoreoisomeric mixtures of the complex [PtIMe3{kappa(2)-Ph2P(C6H4)CH=NCH(Ph)Me-P,N}] (Rc-1) react with AgBF4 and SMePh to give a mixture of complexes [PtMe(SMePh) {kappa(2)-Ph2P(C6H4)CH=NCH(Ph)Me-P,N}]BF4 (2) and [Pt{kappa(2)-Ph2P(C(6)H4)CH=NCH(C6H4)Me-P,N,C}(PhSMe)]BF4 (3) which subsequently render the corresponding chloride compounds [PtClMe{kappa(2)-(R)-Ph2P(C6H4)CH=NCH(Ph)Me-P,N}] (4) and [PtCl{kappa(3)-(R)-Ph2P(C6H4)CH=NCH(C6H4)Me-P,N,C}] (5), by elution with CH2Cl2 on a aluminium oxide chromatography column. Refluxing of [PtIMe3{kappa(2)-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}] (Sc-1) with AgBF4 in a 1:1, CH2Cl2:Me2CO mixture followed by the addition of SMePh, NCMe or pyridine (Py) affords the corresponding cyclometallated compounds [Pt{kappa(3)-(S)-Ph2P(C6H4)CH=NCH(C6H4)Me-P,N,C}(L)]BF4 [L = SMePh (3), NCMe (9), Py (10)]. These compounds have been characterised by analytical and spectroscopic means and by the molecular structure determination of complexes 4 and 10. (C) 2007 Elsevier B.V. All rights reserved.