Kinetic and spectroscopic studies of the substitution reactions of [Rh(acac)(CO)2] with triphenylphosphite

Eldik, Rudi van; Aygen, S.; Kelm, H.; Trzeciak, Anna M.; Ziółkowski, Józef J.

doi:10.1007/bf00620664

Cited by 29 publications

(7 citation statements)

References 7 publications

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“…The catalyst pretreatment is presented in Figure 2 while Figure 3 shows the metal-carbonyl vibration region during hydroformylation until 75 % conversion of 1-decene was reached (see Figure 8). Characteristic steady-state spectra were numbered in Figure 2 to After adding the Rh-precursor to the reactor, characteristic Rh-CO vibrations at α = 2085 cm −1 and β = 2014 cm −1 were observed (spectrum 1) in accordance to the literature [36,39]. Adding the ligand causes the Rh-CO vibrations to disappear rapidly, indicating an almost complete replacement of CO with BiPhePhos at the Rh-center (see Figure 1).…”

Section: Resultssupporting

confidence: 66%

Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step

Jörke

Seidel‐Morgenstern

Hamel

2017

Journal of Molecular Catalysis A: Chemical

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The homogeneously rhodium catalyzed hydroformylation of 1-decene was studied using operando FTIR spectroscopy. The bulky chelating diphosphite ligand BiPhePhos was used for catalyst modification. Special emphasis was given to the transformation of the Rh-precursor Rh(acac)(CO) 2 to the activated HRh(BiPhePhos)(CO) 2 catalyst. Under hydroformylation conditions, this complex was found to be the most abundant catalyst species over a wide range of olefin conversion. Other inactive or non-selective rhodium species were not detectable. Analysis of the turnover frequency revealed a first order dependence of the hydroformylation rate with respect to the concentration of 1-decene. These findings indicate that the coordination of the olefin to the Rh-BiPhePhos catalyst is determining the hydroformylation rate of 1-decene.

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Section: Resultssupporting

confidence: 66%

Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step

Jörke

Seidel‐Morgenstern

Hamel

2017

Journal of Molecular Catalysis A: Chemical

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“…A wide range of mono-and diphosphorous ligands is available to modify Rh-catalysts for an improvement of activity and (regio)selectivity, such as phosphines [4][5][6], phosphonites [7,8] and phosphites [9][10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Hydroformylation and tandem isomerization–hydroformylation of n-decenes using a rhodium-BiPhePhos catalyst: Kinetic modeling, reaction network analysis and optimal reaction control

Jörke

Gaide

Behr

et al. 2017

Chemical Engineering Journal

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The rhodium-BiPhePhos catalyzed hydroformylation of n-decenes, as representative long-chain olefins, was investigated in this study experimentally and theoretically. Besides hydroformylation activity, the used catalyst enables significant double bond isomerization which is an essential side reaction. Because of this property, highly selective tandem isomerization-hydroformylation reactions that convert mixtures of n-decenes with internal double bond position to the desired terminal aldehyde undecanal are possible using the Rh-BiPhePhos catalyst. Experimentally, a reaction network analysis strategy was applied to study the coupled main and side reactions separately. Subsequently, a mechanistic kinetic model based on an extended Wilkinson-mechanism was developed that includes all relevant main and side reactions. Fitting the model to the 23 well planned experiments was possible with low deviations between model and experiment, including the tandem reaction. It was found that the tandem reaction shows completely opposite dependencies regarding temperature and synthesis gas pressure compared to the conventional hydroformylation of 1-decene, which is also covered by the model. Hence, strategies for optimal reaction performance of the (tandem isomerization-)hydroformylation were developed and presented.

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“…When more than 1 equiv of (acac)Rh(CO) 2 was added to 2d an additional doublet became visible in the 31 P NMR spectrum at δ = 117.8 ( J Rh - P = 292 Hz). We assign this signal to the dirhodium complex 4 , which is analogous to the complex (acac)RhCO[P(OPh) 3 ] …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Conformational Behavior of Rhodium(I) Metallohosts Derived from Diphenylglycoluril

Coolen¹,

Leeuwen²,

Nolte³

1996

J. Org. Chem.

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The design and synthesis of molecules containing both a substrate-binding cavity and a nearby catalytically active metal center is a useful approach to the development of synthetic systems that function according to the principles of enzymes. To this end the receptor molecule 2a, derived from diphenylglycoluril, was functionalized with triaryl phosphite ligands to give the receptor ligand 2d. Exchange reactions of 2d with (diketonate)Rh(CO) 2 , (diketone ) acetylacetone, dibenzoylmethane, or dipivaloylmethane) led to the formation of the metallohosts 3a-c, respectively. The properties and conformational behavior of these metal complexes were studied by NMR techniques. Reaction of compounds 3 with H 2 in the presence of a small excess of additional triphenyl phosphite yields the rhodium(I) hydride complex 5. The metallohosts are capable of binding dihydroxybenzene guests in their cavities by hydrogen bonding and π-π stacking interactions. On binding a substrate the conformational behavior of hosts 3a-c was affected considerably.

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Kinetic and spectroscopic studies of the substitution reactions of [Rh(acac)(CO)2] with triphenylphosphite

Cited by 29 publications

References 7 publications

Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step

Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step

Hydroformylation and tandem isomerization–hydroformylation of n-decenes using a rhodium-BiPhePhos catalyst: Kinetic modeling, reaction network analysis and optimal reaction control

Synthesis and Conformational Behavior of Rhodium(I) Metallohosts Derived from Diphenylglycoluril

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