Dormant States of Rhodium Hydroformylation Catalysts: Carboalkoxyrhodium Complex Formed from Enones in the Alkene Feed

Walczuk, Edyta; Kamer, Paul C. J.; Leeuwen, Piet W. N. M. van

doi:10.1002/anie.200351884

Cited by 53 publications

(63 citation statements)

References 22 publications

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“…31 P and 13 C NMR spectra were measured in the 1 H decoupled mode. TMS was used as an external standard for 1 H and 13 C NMR and H 3 PO 4 as an external standard for 31 P NMR. Hydroformylation reactions were carried out in a 200-mL home-made stainless steel autoclave.…”

Section: Experimental Section General Proceduresmentioning

confidence: 99%

“…[6 ± 12] In academia, issues concerning deactivation and decomposition of the catalytic system are rarely addressed. [13] For commercial applications, however, these factors are crucial. Next to catalyst selectivity and activity, stability has been a key issue for the many industrial processes that have come on stream during the last decades.…”

Section: Introductionmentioning

confidence: 99%

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Phenoxaphosphino‐Modified Xantphos‐Type Ligands in the Rhodium‐Catalysed Hydroformylation of Internal and Terminal Alkenes

et al. 2004

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The solubility of the modifying ligand is an important parameter for the efficiency of a rhodiumcatalysed hydroformylation system. A facile synthetic procedure for the preparation of well-defined xanthene-type ligands was developed in order to study the influence of alkyl substituents at the 2-, and 7-positions of the 9,9-dimethylxanthene backbone and at the 2-, and 8-positions of the phenoxaphosphino moiety of ligands 1 ± 16 on solubility in toluene and the influence of these substituents on the performance of the ligands in the rhodium-catalysed hydroformylation. An increase in solubility from 2.3 mmol ¥ L À 1 to > 495 mmol ¥ L À 1 was observed from the least soluble to the most soluble ligand. A solubility of at least 58 mmol ¥ L À 1 was estimated to be sufficient for a large-scale application of these ligands in hydroformylation. Highly active and selective catalysts for the rhodium-catalysed hydroformylation of 1-octene and trans-2-octene to nonanal, and for the hydroformylation of 2-pentene to hexanal were obtained by employing these ligands. Average rates of > 1600 (mol aldehyde) Â (mol Rh)¼ 637 mM} and excellent regio-selectivities of up to 99% toward the linear product were obtained when 1-octene was used as substrate. For internal olefins average rates of > 145 (mol aldehyde) Â (mol Rh)À 1 Â h À 1 {p(CO/ H 2 ) ¼ 3.6 ± 10 bar, T ¼ 393 K, [Rh] ¼ 1 mM, [alkene] ¼ 640 ± 928 mM} and high regio-selectivities up to 91% toward the linear product were obtained.

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Section: Experimental Section General Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Phenoxaphosphino‐Modified Xantphos‐Type Ligands in the Rhodium‐Catalysed Hydroformylation of Internal and Terminal Alkenes

et al. 2004

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“…5 reveals the in situ FT-IR spectrum of the Rh/POL-PPh 3 catalyst adsorbed with a premixing gas (C 2 H 4 :CO:H 2 = 1:1:1). Four peaks of the sample at 2054, 2002, 1992 and 1959 cm −1 are assigned to HRh(CO) 2 (P-frame) 2 species [16,33]. The HRh(CO) 2 (P-frame) 2 compound exists as two trigonal-bipyramidal isomers in equilibrium (one contains two equatorial phosphine ligands; the other contains an equatorial and an apical phosphine ligand).…”

Section: In Situ Ir Analysismentioning

confidence: 99%

Ultrastable 3V-PPh3 polymers supported single Rh sites for fixed-bed hydroformylation of olefins

Jiang

Ding

et al. 2015

Journal of Molecular Catalysis A: Chemical

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“…The effective core potentials (ECP) basis set was used to represent the innermost electrons of the molybdenum and rhodium atoms, and the basis set of double-LANL2DZ was employed for molybdenum and rhodium atoms. The basis set of 6-31G(d, p) was used to model the carbon and hydrogen atoms of the Cp rings and carbon, oxygen atoms of carbonyl groups in the (η 5 -C 5 H 5 )Mo(CO) 3 H, C 5 H 9 CORh(CO) 4 , and the associated hydrogen bonded complexes. The basis function 6-311G (d, p) was used for metal-bound hydrogen.…”

Section: Volume Of Interactionsmentioning

confidence: 99%

Concurrent Synergism and Inhibition in Bimetallic Catalysis: Catalytic Binuclear Elimination, Solute−Solute Interactions and a Hetero-Bimetallic Hydrogen-Bonded Complex in Rh−Mo Hydroformylations

Cheng

Tjahjono

et al. 2010

J. Am. Chem. Soc.

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Hydroformylations of cyclopentene and 3,3-dimethylbut-1-ene were performed using both Rh(4)(CO)(12) and (eta(5)-C(5)H(5))Mo(CO)(3)H as precursors in n-hexane at 298 K. Both stoichiometric and catalytic hydroformylations were conducted as well as isotopic labeling experiments. Six organometallic pure component spectra were recovered from the high-pressure FTIR experiments, namely the known species Rh(4)(CO)(12), (eta(5)-C(5)H(5))Mo(CO)(3)H, RCORh(CO)(4), and the new heterobimetallic complexes RhMo(CO)(7)(eta(5)-C(5)H(5)), a weak hydrogen bonded species (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4), and a substituted RhMo(CO)(7-y)(eta(5)-C(5)H(5))L(y), where y = 1 or 2 and L = (pi-C(5)H(8)). The main findings were (1) catalytic binuclear elimination (CBER) occurs between (eta(5)-C(5)H(5))Mo(CO)(3)H and RCORh(CO)(4) resulting in aldehyde and RhMo(CO)(7)(eta(5)-C(5)H(5)), and this mechanism is responsible for ca. 10% of the product formation; (2) molecular hydrogen is readily activated by the new heterobimetallic complex(es); (3) FTIR and DFT spectroscopic evidence suggests that the weak hydrogen bonded species (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4) has an interaction of the type eta(5)-C(5)H(4)-H...O=C; and (4) independent physicochemical experiments for volumes of interaction confirm that significant solute-solute interactions are present. With respect to the efficiency of the catalytic cycle, the formation of a weak (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4) complex results in a significant decrease in the measured turnover frequency (TOF) and is the primary reason for the inhibition observed in the bimetallic catalytic hydroformylation. Such hydrogen bonding through the eta(5)-C(5)H(5) ring might have relevance to inhibition observed in other catalytic metallocene systems. The present catalytic system is an example of concurrent synergism and inhibition in bimetallic homogeneous catalysis.

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Dormant States of Rhodium Hydroformylation Catalysts: Carboalkoxyrhodium Complex Formed from Enones in the Alkene Feed

Cited by 53 publications

References 22 publications

Phenoxaphosphino‐Modified Xantphos‐Type Ligands in the Rhodium‐Catalysed Hydroformylation of Internal and Terminal Alkenes

Phenoxaphosphino‐Modified Xantphos‐Type Ligands in the Rhodium‐Catalysed Hydroformylation of Internal and Terminal Alkenes

Ultrastable 3V-PPh3 polymers supported single Rh sites for fixed-bed hydroformylation of olefins

Concurrent Synergism and Inhibition in Bimetallic Catalysis: Catalytic Binuclear Elimination, Solute−Solute Interactions and a Hetero-Bimetallic Hydrogen-Bonded Complex in Rh−Mo Hydroformylations

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