The neutral complexes of formula [κ2P,S-(dppmS)Pt(CH 3)(Cl)] (1) and [κ2P,S-(dppeS)Pt(CH 3)(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/CH2C12 affords the corresponding monomeric cationic complexes [κ2P,S- (dppmS)Pt(CH3CN)(CH3)][BF4] (3) and [κ2P,S-(dppeS)Pt(CH3CN)(CH3)][BF 4] (4). Complexes 3 and 4 partially dissociate in CD 2Cl2, 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 CD 2Cl2 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 [K2P,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 6·2CD 2Cl2 are reported. Mass spectrometric analyses with APCI and ESI interfaces were also performed for all new complexes.
Synthesis and carbonylation of platinum(II) organometallic complexes with bis(phosphanyl) monosulfides. Crystal structures of {k2P,S-[Ph2CH2P(S)Ph2]Pt(CH3)(Cl)} and {kP,m-kS-[Ph2CH2CH2P(S)Ph2]Pt-(CH3)}2[BF4]2 / Mmastrorilli, P.; Nobile, Cf.; Suranna, Gp.; Fanizzi, Fp.; Ciccarella, G.; Englert, U.; Li, Q.. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - STAMPA. - 6:(2004), pp. 1234-1242. [10.1002/ejic.200300428]
Synthesis and carbonylation of platinum(II) organometallic complexes with bis(phosphanyl) monosulfides. Crystal structures of {k2P,S-[Ph2CH2P(S)Ph2]Pt(CH3)(Cl)} and {kP,m-kS-[Ph2CH2CH2P(S)Ph2]Pt-(CH3)}2[BF4]2
Nobile, CF.;Suranna, GP.;
2004-01-01
Abstract
The neutral complexes of formula [κ2P,S-(dppmS)Pt(CH 3)(Cl)] (1) and [κ2P,S-(dppeS)Pt(CH 3)(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/CH2C12 affords the corresponding monomeric cationic complexes [κ2P,S- (dppmS)Pt(CH3CN)(CH3)][BF4] (3) and [κ2P,S-(dppeS)Pt(CH3CN)(CH3)][BF 4] (4). Complexes 3 and 4 partially dissociate in CD 2Cl2, 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 CD 2Cl2 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 [K2P,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 6·2CD 2Cl2 are reported. Mass spectrometric analyses with APCI and ESI interfaces were also performed for all new complexes.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.