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

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)

Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes

“…We considered both exo-and endo-substitutions (vide infra). We also chose Pt for further investigations [35,36,110,113,114] due to its prevalence in well-defined organometallic complexes [184][185][186][187] and heterogeneous catalysis [188][189][190][191][192]. Based on the aforementioned studies, only exo-substitution was considered.…”

“…Since discrete organometallic Pt complexes [184,186] and metal surfaces [188,189] are known to undergo coordination or adsorption of carbon monoxide (CO), we imagined that adsorption of CO onto a Pt-doped SWCNT would also be possible [114]. Although the C≡O triple bond is polarized slightly toward the C atom, we considered two possibilities for CO adsorption; namely, C-end adsorption (giving a COadsorbed HSWCNT) and O-end adsorption (giving an OC-adsorbed HSWCNT) were both considered ( Figure 19).…”

(Diphosphane monosulfide)platinum(II) Complexes for Hydroformylation Reactions: Their Catalytic Activity and a High‐Pressure NMR Mechanistic Study

“…Neutral complexes of general formula [κ 2 P,S-(P ∧ PS)Pt(CH 3 )Cl] [P ∧ PS: Ph 2 PCH 2 P(S)Ph 2 , dppmS (1); Ph 2 P(CH 2 ) 2 P(S)Ph 2 , dppeS (2); Ph 2 P(CH 2 ) 3 P(S)Ph 2 , dpppS, (3)] were synthesised by reaction of [(cod)Pt-(CH 3 )(Cl)] (cod = 1,5-cyclooctadiene) with one equivalent of the relevant ligand. [37] (5), in which the sulfur atoms bridge the two platinum atoms, is obtained quantitatively on heating solid 4a at 363 K under vacuum, as described previously. [37] Reaction of [(cod)Pt(CH 3 )(Cl)] with two Figure 1.…”

“…[37] (5), in which the sulfur atoms bridge the two platinum atoms, is obtained quantitatively on heating solid 4a at 363 K under vacuum, as described previously. [37] Reaction of [(cod)Pt(CH 3 )(Cl)] with two Figure 1. Cationic and neutral complexes used in catalysis.…”

“…[32,33] In the framework of our studies into the coordination chemistry of heteroditopic ligands, [34,35] we recently became interested in the monosulfides of diphosphane ligands (P ∧ PS) [36] and have studied the synthesis and reactivity of neutral and cationic methyl complexes of platinum() with the P ∧ PS heteroditopic ligands dppmS and dppeS. [37] The heteroditopic behaviour of the diphosphane monosulfide (P ∧ PS) ligands has recently been exploited in Rhand Ir-catalysed methanol carbonylation. [38,39] Considerably less attention has been paid to the use of Pt complexes of heteroditopic ligands as catalysts for olefin hydroformylation.…”