100333-94-6Relevant articles and documents
Efficient rhodium catalysts for the hydrogenolysis of thiophenic molecules in homogeneous phase
Bianchini, Claudio,Casares, Juan A.,Meli, Andrea,Sernau, Volker,Vizza, Francesco,Sanchez-Delgado, Roberto A.
, p. 3099 - 3114 (2008/10/09)
In the presence of strong bases, the C - S insertion complexes (triphos)Rh[η3-S(C6H4)CH=CH2] and (triphos)Rh(η3-SCH=CHCH=CH2) as well as the π-alkyne complex [(triphos)Rh(η2-MeO
η3-MeC(CH2PPh2)3/rhodium complexes utilize phosphine arm dissociation mechanisms at 25°C
Thaler, Eric G.,Folting, Kirsten,Caulton, Kenneth G.
, p. 2664 - 2672 (2007/10/02)
Reaction of RhMe3(triphos) (triphos = MeC(CH2PPh2)3) with CO generates acetone and RhMe(CO)(triphos), which reacts with further CO to give Rh[C(O)Me](CO)(triphos). The structure of RhMe(CO)(triphos) shows one strained P-Rh-P bond angle between equatorial ligands (90.80 (5)°) in a trigonal bipyramid, together with intramolecular steric effects that cause a small equatorial CO-Rh-axial(CH3) C/C angle of 79.09 (25)°. The acetyl and methyl complexes react with H2 at 25°C to produce acetaldehyde and methane, respectively, together with RhH(CO)(triphos). Reaction of CO with RhH3(triphos) is even faster than with RhMe3(triphos) to give H2 and RhH(CO)(triphos), together with a CO hydrogenation product. These results show that these clean stoichiometric conversions, as well as a variety of isotopic exchange reactions of the Rh(I) and Rh(III) compounds with D2 and 13CO, occur by preequilibrium dissociation of one arm of the triphos ligand at 25°C. One such species, Rh[C(O)Me](CO)2(η2-triphos), is directly detectable and reveals the mechanism of exchange of Rh[C(O)Me](13CO)(triphos) with 12CO. The coordination of CO to Rh(H)3(η2-triphos) is proposed to generate a dihydrogen complex, thus accounting for the CO-induced elimination of H2. As suggested by these individual reactions, RhH(CO)(triphos) is a catalyst for olefin hydroformylation. The high n:iso selectivity mimics that of RhH(CO)(PPh3)3 in the presence of a large amount of added PPh3, a beneficial consequence of the chelate effect.
Rhodium Complexes with the Tripodal Triphosphine MeC(CH2PPh2)3 as Highly Reactive Systems for Hydrogenation and Hydroformylation of Alkenes
Bianchini, Claudio,Meli, Andrea,Peruzzini, Maurizio,Vizza, Francesco,Fujiwara, Yuzo,et al.
, p. 299 - 301 (2007/10/02)
The (triphos)Rh fragment is able to form strong bonds with several reactive species (hydride, alkyl, carbon monoxide, alkenes), some reactions of which are highly specific; preliminary results on the hydrogenation and hydroformylation of hex-1-ene using (triphos)RhH(C2H4) as catalyst precursor are discussed.
