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

Abstract

Abstract The neutral complexes of formula [κ 2 P , S ‐(dppmS)Pt(CH 3 )(Cl)] ( 1 ) and [κ 2 P , S ‐(dppeS)Pt(CH 3 )(Cl)] ( 2 ) [dppmS = Ph 2 PCH 2 P(S)Ph 2 , dppeS = Ph 2 P(CH 2 ) 2 P(S)Ph 2 ] have been synthesised and characterised. Reaction of 1 and 2 with AgBF 4 carried out in CH 3 CN or CH 3 CN/CH 2 Cl 2 affords the corresponding monomeric cationic complexes [κ 2 P , S ‐(dppmS)Pt(CH 3 CN)(CH 3 )][BF 4 ] ( 3 ) and [κ 2 P , S ‐(dppeS)Pt(CH 3 CN)(CH 3 )][BF 4 ] ( 4 ). Complexes 3 and 4 partially dissociate in CD 2 Cl 2 , giving, in the case of 3 , the asymmetric dimer {[κ 2 P , S ‐(dppmS)](CH 3 )Pt{κ P ,μ‐κ S ‐(dppmS)}Pt(CH 3 )(CH 3 CN)][BF 4 ] 2 ( 5 ), and, in the case of 4 , the symmetrical sulfur‐bridged dimer [κ P ,μ‐κ S ‐(dppeS)Pt(CH 3 )] 2 [BF 4 ] 2 ( 6 ). Pure 6 can be obtained by heating 4 under vacuum. Exposing CD 2 Cl 2 solutions of the cationic complexes 3 and 4 to CO at ambient conditions brings about the formation of the monomeric methyl carbonyl complexes [κ 2 P , S ‐(dppmS)Pt(CO)(CH 3 )][BF 4 ] (CO trans to P, 7a ) and [κ 2 P , S ‐(dppeS)Pt(CO)(CH 3 )][BF 4 ] (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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)