15318-31-7Relevant articles and documents
Systematic Study of the Stereoelectronic Properties of Trifluoromethylated Triarylphosphines and the Correlation of their Behaviour as Ligands in the Rh-Catalysed Hydroformylation
Herrera, Daniel,Peral, Daniel,Cordón, Mercedes,Bayón, J. Carles
supporting information, p. 354 - 363 (2020/12/30)
The stereoelectronic properties of a series of trifluoromethylated aromatic phosphines have been studied using different approaches. The σ-donating capability has been evaluated by nuclear magnetic resonance (NMR) spectroscopy of the selenide derivatives and the protonated form of the different trifluoromethylated phosphines. The coupling constants between phosphorous and selenium (1JSeP) and phosphorous and hydrogen (1JHP) can be predicted by empirical equations and correlate the basicity of the phosphines with the number and relative position of trifluoromethyl groups. In contrast, the π-acceptor character of the ligands has been evaluated by measuring the frequency of the CO vibration in the infrared (IR) spectra of the corresponding Vaska type iridium complexes ([IrCl(CO)(PAr3)2], PAr3=triarylphosphine). Moreover, the correlation between the electronic properties and the performance of these phosphines as ligands in the rhodium-catalysed hydroformylation of 1-octene has been established. Phosphines with the lowest basicity, that are those with the highest number of trifluoromethyl groups, gave rise to more active catalytic systems.
Phosphine, isocyanide, and alkyne reactivity at pentanuclear molybdenum/tungsten-iridium clusters
Simpson, Peter V.,Randles, Michael D.,Gupta, Vivek,Fu, Junhong,Moxey, Graeme J.,Schwich, Torsten,Morshedi, Mahbod,Cifuentes, Marie P.,Humphrey, Mark G.
supporting information, p. 7292 - 7304 (2015/04/27)
The trigonal bipyramidal clusters M2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me4R) (M = Mo, R = Me 1a, R = H; M = W, R = Me, H) reacted with iso
Slow exchange of bidentate ligands between rhodium(I) complexes: Evidence of both neutral and anionic ligand exchange
Chen, Si,Manoury, Eric,Poli, Rinaldo
, p. 5820 - 5826 (2015/02/19)
The phosphine double exchange process involving [RhCl(COD)(TPP)] and [Rh(acac)(CO)(TMOPP)] (TPP = PPh3, TMOPP = P(C6H4-4-OMe)3) to yield [RhCl(COD)(TMOPP)] and [Rh(acac)(CO)(TPP)] is very rapid but is followed by a much slower process where the bidentate ligands are exchanged to yield [Rh(acac)(COD)] and a mixture of [RhCl(CO)(TPP)2], [RhCl(CO)(TMOPP)2], and [RhCl(CO)(TPP)(TMOPP)]. The exchange involving [RhCl(COD)(L)] and [Rh(acac)(CO)(L)] yields [Rh(acac)(COD)] and [RhCl(CO)(L)2], where the reaction is much faster when L = TPP than when L = TMOPP. The mixed-metal system comprising [IrCl(COD)(TPP)] and [Rh(acac)(CO)(TPP)] yields all four complexes [M(acac)(COD)] and [MCl(CO)(TPP)2], where M = Rh and Ir. This illustrates that both a neutral ligand exchange and an anionic ligand exchange occur. Possible pathways for these processes are discussed.
