258874-56-5

Upstream product

• 143006-27-3 (1,2-bis(bis(pentafluorophenyl)phosphino)ethane)dichloroplatinum(II) 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 1493-13-6 trifluorormethanesulfonic acid 

Relevant academic research and scientific papers

Mechanistic studies of the hydroamination of norbornene with electrophilic platinum complexes: The role of proton transfer

Hydroaminations of norbornene with arylsulfonamides and weakly basic anilines were achieved using electrophilic Pt(II) bis(triflate) complexes of the type L2Pt(OTf)2 (L2 = tBu 2bpy, tBuC6H4N= C(CH 3)C(CH3)=NC6H4tBu, (C6H5)2PCH2CH2P(C 6H5)2, (C6F5) 2PCH2CH2P(C6F5) 2, S-BINAP). Pseudo-first-order kinetics reveal little to no dependence of the reaction rate on the ancillary ligand. Mechanistic studies do not favor an olefin coordination mechanism but are instead consistent with a mechanism involving sulfonamide coordination and generation of an acidic proton that is transferred to the norbornene. It is postulated that the resulting norbornyl cation is then attacked by free sulfonamide, and loss of proton from this adduct completes the hydroamination. The platinum-sulfonamide complex readily undergoes deprotonation to give μ-amido platinum-bridged dimer that was isolated from the reaction solution. These studies also involve use of Me3SiPh and Me3SnPh as non-nucleophilic proton traps. Cleavage of the Ph-E bonds was used to detect the acidic, catalytically active species.

Metal-alkyl bond protonolysis studies of (dfepe)Pt(Me)X complexes in acidic media

Protonolyses of (dfepe)Pt(Me)X (dfepe = (C2F5)2PCH2CH2P(C 2F5)2; X = O2CCF3, OSO2H, OSO2CF3, OSO2F) complexes in their respective neat acid solutions cleanly yield (dfepe)-Pt(X)2 products with rates dependent on relative acid strengths. No (dfepe)Pt(Me)(X)2(H)+ intermediates were observed by variable-temperature NMR in dichloromethane. The (perfluoroaryl)phosphine analogue (dfppe)Pt(Me)2 (dfppe = (C6F5)2PCH2CH2P(C 6F5)2) is much less resistant to protonolysis and rapidly converts to (dfppe)Pt(OTf)2 in HOTf at 20°C. Kinetic studies for protonolysis in CF3CO2H(D) and CF3SO3H(D) solvents were carried out. Examination of ionic strength and chloride anion effects in trifluoroacetic acid indicate that prior association of anion to (dfepe)Pt(Me)X systems is not kinetically important. kH/kD values were obtained from competitive protonolysis studies (CF3CO2H, 9 ± 2 (20°C); H2SO4, 7 ± 2 (100°C); CF3SO3H, 2.7 ± 0.7 (100°C)). In the case of CF3CO2H, separate kinetic runs in protio and deuterio acids gave a lower kH/kD value of 3.6(4). The data obtained in these studies do not differentiate between limiting SE2 and SE(oxidative) protonolysis mechanisms.