Synthesis and carbonylation of platinum(II) organometallic complexes with bis(phosphanyl) monosulfides - Crystal structures of [kappa P-2,S-Ph2CH2P(S)Ph-2Pt(CH3)(Cl)] and [kappa P,mu-kappa S-Ph2CH2CH2P(S)Ph-2Pt(CH3)](2)[BF4](2)

The neutral complexes of formula [kappa(2)P,S-(dppmS)Pt(CH3)(Cl)] (1) and [kappa(2)P,S-(dppeS)Pt(CH3)(Cl)] (2) [dppmS = Ph2PCH2P(S)Ph-2, dppeS = Ph2P(CH2)(2)P(S)Ph-2] have been synthesised and characterised. Reaction of 1 and 2 with AgBF4 carried out in CH3CN or CH3CN/CH2Cl2 affords the corresponding monomeric cationic complexes [kappa(2)P,S-(dppmS)Pt(CH3CN)(CH3)][BF4] (3) and [kappa(2)P,S-(dppeS)Pt(CH3CN)(CH3)][BF4] (4). Complexes 3 and 4 partially dissociate in CD2Cl2, giving, in the case of 3, the asymmetric dimer {[kappa(2)P,S-(dppmS)](CH3)Pt{kappaP,mu-kappaS-(dppmS)}Pt(CH3)(CH3CN)][BF4](2) (5), and, in the case of 4, the symmetrical sulfur-bridged dimer [kappaP,mu-kappaS-(dppeS)Pt(CH3)](2)[BF4](2) (6). Pure 6 can be obtained by heating 4 under vacuum. Exposing CD2Cl2 solutions of the cationic complexes 3 and 4 to CO at ambient conditions brings about the formation of the monomeric methyl carbonyl complexes [kappa(2)P,S-(dppmS)Pt(CO)(CH3)][BF4] (CO trans to P, 7a) and [kappa(2)P,S-(dppeS)Pt(CO)(CH3)][BF4] (CO trans to P, 8a), which slowly transform into their CO cis to P isomers 7b and 8b, respectively. The single-crystal X-ray diffraction studies of 1(.)CD(2)Cl(2) and 6(.)2CD(2)Cl(2) are reported. Mass spectrometric analyses with APCI and ESI interfaces were also performed for all new complexes.