436149-53-0Relevant academic research and scientific papers
Hydroformylation of 1-hexene and propene with in situ formed rhodium phosphine catalysts
Pakkanen,Reinius,Riihimaeki,Suomalainen,Krause,Laitinen,Jaeaeskelaeinen,Pursiainen,Haukka
, p. 67 - 78 (2001)
A series of triphenylphosphines modified with different heteroatom groups (-SCH3, -N(CH3)2, -OCH3, -CF3) in ortho or para position of the phenyl ring was synthesized, and their catalytic behavior in the rhodium catalyzed hydroformylation of 1-hexene (80°C, 15 bar) and propylene (100°C, 10 bar) were studied. The effect of in situ introduced ligands varied with reacting alkene. In the case of 1-hexene, the differences in activity and in chemo- and regioselectivity obtained with various ligands were minor. With propylene, the heterodonor bidentate ligands suppressed the hydroformylation reaction. A similarity between 1-hexene and propylene was observed with CF3 modified ligands. Isomerization was the main reaction in 1-hexene hydroformylation. The strong σ-donor ligands yielded higher hydroformylation activity than the less basic ligands. In the case of propylene, 1,4-bis(diphenylphosphino)butane and (o-thiomethylphenyl)bis(1-naphthyl)phosphine favored the formation of n-butanal.
Synthesis and coordination chemistry of ortho-perfluoroalkyl-derivatised triarylphosphines
Croxtall, Ben,Fawcett, John,Hope, Eric G.,Stuart, Alison M.
, p. 491 - 499 (2007/10/03)
In order to establish the steric and electronic effects of fluorous ponytails in the ortho-positions of triarylphosphines the two novel phosphines, PPh2(2-C6H4C6F 13) II and P(4-C6H4C6F13)2 (2-C6H4C6F13) V, have been synthesised and their coordination chemistry investigated and compared with that of the ortho-trifluoromethyl-derivatised ligand, PPh2(2-C6H4CF3) VI. The single crystal X-ray structures of Ph2P(O)(2-C6H4C6F13) and Ph2P(O)(2-C6H4CF3), along with that of PPh2(2-C6H4CF3), are reported and compared with each other. The large steric influence of the ortho-trifluoromethyl and -perfluorohexyl substituents results in the formation of the, normally, less-thermodynamically favoured trans-[PtCl2L2] complexes. Analysis of the single crystal X-ray structures of trans-[PtCl2{PPh2(2-C6H4CF 3)}2] 1, trans-[PtCl2{PPh2(2-C6H4C 6F13)}2] 2 and trans-[RhCl(CO){PPh2(2-C6H4CF3)} 2] 4 reveals a larger cone angle for PPh2(2-C6H4CF3) (169°) than for PPh2(2-C6H4C6F13). An average cone angle of 166° was calculated for the latter phosphine with values ranging from 164 to 168°.
