Synthesis and Carbonylation of Platinum(II) Organometallic Complexes with Bis(phosphanyl) Monosulfides − Crystal Structures of [κ2P,S-{Ph2CH2P(S)Ph2}Pt(CH3)(Cl)] and [κP,μ-κS-{Ph2CH2CH2P(S)Ph2}Pt-(CH3)]2[BF4]2

• Published in: European journal of inorganic chemistry 2004-03, Vol.2004 (6), p.1234-1242
• Main Authors: Mastrorilli, Piero, Nobile, Cosimo F., Suranna, Gian P., Fanizzi, Francesco P., Ciccarella, Giuseppe, Englert, Ulli, Li, Qi
• Format: Article
• Language: English
• Subjects: Bridging ligands; Carbonyl ligands; Mass spectrometry; P,S ligands; Platinum; S ligands
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200300428

The neutral complexes of formula [κ2P,S‐(dppmS)Pt(CH3)(Cl)] (1) and [κ2P,S‐(dppeS)Pt(CH3)(Cl)] (2) [dppmS = Ph2PCH2P(S)Ph2, dppeS = Ph2P(CH2)2P(S)Ph2] 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 [κ2P,S‐(dppmS)Pt(CH3CN)(CH3)][BF4] (3) and [κ2P,S‐(dppeS)Pt(CH3CN)(CH3)][BF4] (4). Complexes 3 and 4 partially dissociate in CD2Cl2, giving, in the case of 3, the asymmetric dimer {[κ2P,S‐(dppmS)](CH3)Pt{κP,μ‐κS‐(dppmS)}Pt(CH3)(CH3CN)][BF4]2 (5), and, in the case of 4, the symmetrical sulfur‐bridged dimer [κP,μ‐κS‐(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 [κ2P,S‐(dppmS)Pt(CO)(CH3)][BF4] (CO trans to P, 7a) and [κ2P,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·CD2Cl2 and 6·2CD2Cl2 are reported. Mass spectrometric analyses with APCI and ESI interfaces were also performed for all new complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)