Rhodium-diphosphine tosylate complexes as hydrogenation catalysts

1986 ◽  
Vol 51 (2) ◽  
pp. 340-346 ◽  
Author(s):  
Jiří Reiss ◽  
Jiří Hetflejš
Keyword(s):  
Rhodium Complexes ◽  
Hydrogenation Catalysts ◽  
Catalytic Behaviour ◽  
High Yields ◽  
Model Reactions

Novel rhodium-diphosphine tosylate complexes of the type [Rh(COD)L2]+ (O3SC6H4CH3-p)- (L2 = diphos, prophos, buphos, (-)-DIOP) have been prepared in high yields (87-92%) by the displacement of acac ligand from Rh(COD)(acac)by p-toluenesulphonic acid in the presence of L2. The complexes were found to be efficient hydrogenation catalysts comparable in activity to know cationic rhodium complexes. Some differences in the catalytic behaviour of both systems are reported, using hydrogenation of 1-octene and Z-α-acetamidocinnamic acid as model reactions.

scholarly journals Platinum and rhodium complexes ligated by imidazolium-substituted phosphine as efficient and recyclable catalysts for hydrosilylation

RSC Advances ◽  
2019 ◽  
Vol 9 (50) ◽  
pp. 29396-29404 ◽  
Author(s):  
Magdalena Jankowska-Wajda ◽  
Olga Bartlewicz ◽  
Andrea Szpecht ◽  
Adrian Zajac ◽  
Marcin Smiglak ◽  
...  
Keyword(s):  
Rhodium Complexes ◽  
Recyclable Catalysts ◽  
High Yields

Platinum and rhodium complexes ligated by imidazolium substituted phosphine were obtained with high yields and applied as efficient catalysts.

Ruthenium- and Rhodium-Catalyzed Ring-Opening Coupling Reactions of Cyclopropenones with Alkenes or Alkynes

Synlett ◽  
2018 ◽  
Vol 29 (06) ◽  
pp. 717-722 ◽  
Author(s):  
Teruyuki Kondo ◽  
Ryosuke Taniguchi ◽  
Yu Kimura
Keyword(s):  
Carbon Monoxide ◽  
Catalytic Activity ◽  
Methyl Acrylate ◽  
Ring Opening ◽  
Argon Atmosphere ◽  
High Catalytic Activity ◽  
Rhodium Complexes ◽  
Coupling Reactions ◽  
Internal Alkynes ◽  
High Yields

Ru3(CO)12-catalyzed divergent ring-opening coupling reactions of a cyclopropenone with methyl acrylate (an electron-deficient alkene) are developed. Under an argon atmosphere, a decarbonylative linear codimer is obtained, while cyclopentenones are obtained under carbon monoxide (20 atm) without decarbonylation. While ruthenium complexes show no catalytic activity for the ring-opening cocyclization of cyclopropenones with ethylene (20 atm) or bicyclo[2.2.1]hept-2-ene (2-norbornene), rhodium complexes, especially [RhCl(η4-1,5-cod)]2, show high catalytic activity for the desired cocyclization reactions to give the corresponding cyclopentenones in high yields and selectivities. In addition, [RhCl(η4-1,5-cod)]2 realizes the catalytic ring-opening co­cyclization of cyclopropenones with internal alkynes to give the corresponding cyclopentadienones. In all these reactions, ruthena- or rhodacyclobutenones are considered to be key intermediates, generated by strain-driven oxidative addition of a cyclopropenone C–C bond to an ­active ruthenium or rhodium species.

Asymmetric Synthesis of Chiral δ-lactones using BINAP-ruthenium(II) Complexes Hydrogenation Catalysts

2002 ◽  
Vol 2002 (11) ◽  
pp. 567-569 ◽  
Author(s):  
Yanjun Li ◽  
Taeko Izumi
Keyword(s):  
Asymmetric Synthesis ◽  
Ruthenium Complexes ◽  
Asymmetric Hydrogenation ◽  
Optical Purity ◽  
Hydrogenation Catalysts ◽  
Keto Acids ◽  
Chiralcel Od ◽  
High Yields

Asymmetric hydrogenation of keto-acids was accomplished by catalytic amounts of BINAP-ruthenium complexes to afford the corresponding δ-lactones in high yields. The optical purity of the synthesised δ-lactones was determined by chiralcel (OD) in the 9–56% range.

Rhodium complexes with phosphine and diazabutadiene ligands. Their properties as hydrogenation catalysts. Molecular structure of RhCl(COD)P(p-C6H4F)3

1987 ◽  
Vol 127 (2) ◽  
pp. 215-221 ◽  
Author(s):  
M. Iglesias ◽  
C. Del Pino ◽  
A. Corma ◽  
S. Garcia-Blanco ◽  
S. Martinez Carrera
Keyword(s):  
Molecular Structure ◽  
Rhodium Complexes ◽  
Hydrogenation Catalysts

Chiral Rhodium Complexes Derived From Electron-Rich Phosphine-Phosphites as Asymmetric Hydrogenation Catalysts

2011 ◽  
Vol 30 (24) ◽  
pp. 6718-6725 ◽  
Author(s):  
Pablo Etayo ◽  
José L. Núñez-Rico ◽  
Anton Vidal-Ferran
Keyword(s):  
Asymmetric Hydrogenation ◽  
Rhodium Complexes ◽  
Hydrogenation Catalysts

Rh2Cl2(CO)4 adsorbed and tethered on gold powder: IR spectroscopic characterization and olefin hydrogenation activity

2001 ◽  
Vol 79 (5-6) ◽  
pp. 578-586 ◽  
Author(s):  
Hanrong Gao ◽  
Robert J Angelici
Keyword(s):  
Spectroscopic Characterization ◽  
Rhodium Complexes ◽  
Olefin Hydrogenation ◽  
Hydrogenation Catalysts ◽  
Gold Powder ◽  
Ir Studies ◽  
Major Species ◽  
Catalytically Active ◽  
Unidentified Species ◽  
Diffuse Reflectance Infrared

Catalysts were prepared by adsorbing Rh2Cl2(CO)4 directly on gold powder or on gold that contained the tethered ligands 2-(diphenylphosphino)ethane-1-thiol (DPET) or methyl 2-mercaptonicotinate (MMNT). Infrared (IR) studies (diffuse reflectance infrared Fourier transform (DRIFT)) of the catalyst Rh–Au prepared by adsorbing Rh2Cl2(CO)4 directly on Au indicate that a RhI(CO)2 species is present. IR studies of Rh–DPET-Au suggest that tethered cis-Rh(DPET)(CO)2Cl is the major species at relatively high Rh2Cl2(CO)4 loadings, but trans-Rh(DPET)2(CO)Cl is observable at low Rh2Cl2(CO)4 loadings. Spectral investigations of the catalyst Rh–MMNT-Au prepared by adsorbing Rh2Cl2(CO)4 on MMNT-Au suggest that tethered [cis-Rh(MMNT)2(CO)2]+Cl– and (or) Rh(MMNT)(CO)2Cl are the major species at low Rh2Cl2(CO)4 loadings, while a new unidentified species predominates at high Rh2Cl2(CO)4 loadings. All three catalysts are active 1-hexene hydrogenation catalysts under the mild conditions of 40°C and 1 atm of H2; they are much more active than Au powder or Rh2Cl2(CO)4 in solution. Of the three catalysts, Rh–Au is the most active with a maximum turnover frequency (TOF) of 800 mol H2 per mol Rh per min while its turnover (TO) is 29 600 mol H2 per mol Rh during a 2-hour run. Under the conditions of 1-hexene hydrogenation, the catalysts lose their CO ligands. Thus, it appears that a form of Rh metal on Au is the catalytically active species.Key words: catalysis, olefin hydrogenation, gold powder, tethered rhodium complexes, infrared studies, adsorption, rhodium complexes.

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