200426-55-7

Upstream product

• 26042-63-7 silver(I) hexafluorophosphate 
• 33847-53-9 chloro-η(3)-(bis(diphenylphosphinoethyl)phenylphosphine)rhodium(I) 
• 201230-82-2 carbon monoxide 
• 60969-19-9 thallium(I) hexafluorophosphate 

Downstream Products

• 223915-50-2 Rh(bis(2-diphenylphosphinoethyl)phenyl phosphine)(OC₆H₄-p-Me) 
• 223929-62-2 mer-[Rh(bis(2-diphenylphosphinoethyl)phenyl phosphine)(CO)(OC₆H₄-p-Me)] 
• 223929-62-2 fac-[Rh(bis(2-diphenylphosphinoethyl)phenyl phosphine)(CO)(OC₆H₄-p-Me)] 
• 33847-53-9 chloro-η(3)-(bis(diphenylphosphinoethyl)phenylphosphine)rhodium(I) 
• 223929-61-1 fac-[Rh(bis(2-diphenylphosphinoethyl)phenyl phosphine)(CO)(OPh)] 
• 200427-32-3 [Rh(bis(2-diphenylphosphinoethyl)phenyl phosphine)(CO)2]PF₆ 
• 200427-32-3 Rh(CO)2(C₃₄H₃₃P₃)⁽¹⁺⁾*PF₆^(1-) = [Rh(CO)2(C₃₄H₃₃P₃)]PF₆ 
• 200427-18-5 Rh(CO)(C₃₄H₃₃P₃)⁽¹⁺⁾*B(C₆H₅)4^(1-) = [Rh(CO)(C₃₄H₃₃P₃)]B(C₆H₅)4 

Relevant academic research and scientific papers

IR spectroscopic studies of the reversible equilibria between Rh(I)(triphos) aryloxides, aryloxycarbonyls, and carbonyls

The complex, [Rh(triphos)CO][PF6] {triphos = bis(2-diphenylphosphinoethyl)phenyl phosphine}, 4, reacts with aryloxides, ArO- {Ar = C6H5, C6H4-p-CH3, C6H4-p-OCH3}. The formation and subsequent chemistry of the resulting aryloxycarbonyl complexes were observed by FTIR spectroscopy. These aryloxycarbonyl complexes are formed and decay via different pathways involving the fac- and mer-isomers of Rh(triphos)(CO)(OAr). Decarbonylation of Rh(triphos)(CO)(OAr) forms Rh(triphos)OAr, {Ar = C6H5 (1), C6H4-p-CH3, (2) C6H4-p-OCH3 (3)}, while elimination of the aryloxide via a different pathway can also reform [Rh(triphos)CO][PF6], 4.

1-Hexene hydroformylation with the rhodium(I) triphosphane complex [Rh(CO){PhP(CH2CH2PPh2)2}]PF 6: An in situ study using high-pressure NMR spectroscopy

The rhodium-catalyzed hydroformylation of 1-hexene in THF with the linear triphosphane PhP(CH2CH2PPh2)2 [PP2] has been studied both in situ and in high-pressure autoclaves. Sapphire NMR tubes with titanium valves have proved useful for studying the in situ reactions under conditions of relatively high syngas pressure (30-90 atm H2/CO) and temperature (60-100 °C). Under conditions conducive to effective hydroformylation, the catalyst precursor [(PP2)Rh(CO)]+ is quantitatively converted to the dicarbonyl [(PP2)Rh(CO)2]+, which is also the termination product of the catalysis. Irrespective of the syngas composition and of the total pressure, the dicarbonyl complex is the only phosphorus-containing species detectable on the NMR time-scale during the course of the isomerization and hydroformylation of the alkene. The PP2-Rh catalytic system exhibits some peculiar features that may be summarized as follows, (i) Very high partial pressures of CO (120 atm) neither inhibit the hydroformylation nor af-feet the n/i selectivity; (ii) alkene hydrogenation occurs neither at very high partial pressures of H2 (120 atm) nor in the absence of added CO; (iii) the isomerization rate is slightly faster than that of hydroformylation; (iv) terminal and internal alkenes (2-, 3-hexenes) are hydroformylated with comparable rates. Various control experiments have been carried out using in-situ NMR, as well as batch experiments under different reaction conditions or with different catalyst precursors. Despite these extensive studies, unambiguous conclusions about the catalysis mechanism have not been reached. In particular, the possibility that different catalysts may be operative depending on the reaction conditions cannot be ruled out. The hydroformylation results rule out the involvement of phosphane-free "Rh-CO" catalysts, even under conditions of very high partial pressure of CO, and point to "(PP2)Rh(CO)x" catalysts with small steric hindrance over the whole range of syngas pressures investigated. WILEY-VCH Verlag GmbH, 1997.