Rhodium-calix[6]arene diphosphite complex as olefin hydroformylation catalyst

Караханов, Э. А.; Kardasheva, Yu. S.; Runova, E. A.; Sakharov, D. A.; Terenina, M. V.

doi:10.1134/s0965544106040062

Cited by 11 publications

(9 citation statements)

References 19 publications

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“…8, 23 The data on non 1 ene hydroformylation in the pres ence of ligands L 1 -L 7 under identical conditions are presented in Table 1. It is seen that the catalytic systems based on calix [6]arenes are characterized by the highest activity.…”

Section: Methodsmentioning

confidence: 99%

“…The L 6 macrocycle was obtained in the cone conformation. 23 In The 31 P NMR spectrum of dipropoxycalix [4]arene phosphinite L 3 exhibits the single signal as a singlet the 1 H NMR spectrum of the L 7 calixarene, the group of doublet signals of the bridging methylene protons (δ 3.52-4.78) indicates that they are nonequivalent and, hence, the macrocycle molecule is not symmetric, which is confirmed by two singlets in the 31 P NMR spectrum (103.4 and 103.9 ppm, 1 J P,P = 93 Hz). The mass spectra (ESI) of compounds L 6 and L 7 contain only the [M] + signals (m/z 1029 and 693, respectively).…”

Section: R = H Bu Tmentioning

confidence: 97%

“…The mass spectra (ESI) of compounds L 6 and L 7 contain only the [M] + signals (m/z 1029 and 693, respectively). The NMR and mass spectrometry studies of the reac tions of diphosphites L 6 and L 7 with Rh(acac)(CO) 2 and [Rh(COD)Cl] 2 (COD is cycloocta 1,5 diene) in solu tion at different calix/metal ratios 8, 23 show that at P/Rh = 2 (equimolar amounts of rhodium and calixare ne) the rhodium atom is bound to one macrocyclic ligand. The further increase in the calixarene content in a solu tion (twofold and higher molar excess of cyclophane) results in the predominant formation of the RhL 2 com plex in which two bulky macrocycles are coordinated to the metal center.…”

Section: R = H Bu Tmentioning

confidence: 99%

“…O Phosphorylated calixarenes L 1 -L 5 (see Refs 5,23,and 24) were synthesized by the successive interaction of the corresponding calixarenes with n butyllithium and diphenylchlorophosphine (Scheme 2).…”

Section: Hydroformylation Of Unsaturated Compounds Using Calixarene Bmentioning

confidence: 99%

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Design of supramolecular metal complex catalytic systems for petrochemical and organic synthesis

et al. 2008

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Specific features of the behavior of the supramolecular metal complex catalysts based on calix arenes, cyclodextrins, and dendrimers in the reactions of hydroformylation, Wacker oxidation, hydroxylation of aromatics, 2 naphthol coupling, and oxidative coupling of styrenes and benzene were studied. The factors affecting the catalytic activity and selectivity are discussed.The control of selectivity in catalytic systems is one of the main problems in petrochemical and organic synthe ses. In the recent years researchers are interested in su pramolecular catalysis, the phenomena based on the use of substances capable of forming host-guest inclusion complexes with various organic compounds as compo nents of catalytic systems. This approach provides wide possibilities for design of new highly active metal com plex catalysts with high substrate, regio , and chemiose lectivity. 1-7Various classes of receptor molecules, particularly, cyclodextrins, calixarenes, and dendrimers ( Fig. 1), are used for the design of supramolecular catalysts. 2-4,8,9Cyclodextrins are macrocyclic compounds formed by α D glucopyranose. Calixarenes are the compounds syn thesized by the condensation of phenols and aldehydes of diverse structure. The selective functionalization of the upper and lower rims of these macrocycles by hetero atomic groups can form a molecular system bearing sev eral binding sites and in this way create catalysts capable of molecular recognition. One more type of molecular receptors is presented by dendrimers, which are polymer molecules with regular branched structures and can be considered as unique monomolecular globular micelles. Due to noncovalent interactions between several frag ments of the polymer chain and an organic molecule, dendrimers can be selectively bonded to the substrate, thus enhancing the efficiency and selectivity of the im mobilized metal complex catalyst. 3,9-18 Location of the active sites at the ends of the dendrimer branches can minimize diffusional restrictions, and the den drimers become good models for studying specific fea tures of the behavior of the immobilized homogeneous systems.Design of the catalysts on the basis of receptor mole cules can be performed via two routes: (1) using the target chemical modification of the receptor acting as a ligand;(2) using the molecular imprinting method. 3 The im printing process proceeds as follows. At the first step a receptor molecule interacts with a template molecule to form a host-guest inclusion complex (Scheme 1). The structure that formed is immobilized by binding agents containing two and more functional groups. At the Scheme 1

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Section: Methodsmentioning

confidence: 99%

Section: R = H Bu Tmentioning

confidence: 97%

Section: R = H Bu Tmentioning

confidence: 99%

Section: Hydroformylation Of Unsaturated Compounds Using Calixarene Bmentioning

confidence: 99%

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Design of supramolecular metal complex catalytic systems for petrochemical and organic synthesis

et al. 2008

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“…The group of Karakhanov studied two bis‐phosphites 33 and 34 as ligand in styrene hydroformylation (Figure ). [19b], With theses compounds, the two phosphorus atoms are capping three oxygen atoms of a calix[6]arene skeleton. The catalytic tests were carried out in toluene at 50 °C using [Rh(acac)(CO) 2 ], as metal precursor and excess of ligand.…”

Section: Rhodium‐catalyzed Styrene Hydroformylationmentioning

confidence: 99%

Styrene Hydroformylation with Cavity‐Shaped Ligands

Bauder

Sémeril

2019

Eur J Inorg Chem

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The goal of this review is to give an up-to-date overview of phosphorus(III)-functionalized calixarenes, resorcinar-Scheme 1. Hydroformylation of α-olefins with side reactions. [a] David Sémeril is a "Chargé de recherche" within the CNRS. After a PhD in catalysis under the supervision of Dr. C. Bruneau and Prof. P. H. Dixneuf in Rennes, he carried out postdoctoral studies in Pisa on polymer chemistry with Prof. F. Ciardelli, then in Florence with Dr. C. Bianchini, where he developed several active polymerization catalysts based on conformationally restricted ligands. He joined the CNRS in 2003 within the laboratory of Dr. D. Matt in Strasbourg, where he has actively developed a research program on the application of ligands derived from molecular cavities (calixarenes and resorcinarenes) in homogeneous catalysis. He passed his habilitation qualification in 2008 and his most remarkable recent results concern highly selective hydroformylation catalysts and efficient supramolecular catalysts, all based on macrocyclic skeletons. He was awarded the Gineste Prize (University of 4951 enes and cyclodextrins as ligands for rhodium-and platinumcatalyzed styrene hydroformylation. Scheme 2. Equilibrium between rhodium species. Scheme 3. Catalytic cycle for styrene hydroformylation.Figure 1. Generic calix[n]arenes (A), cyclodextrins (α-CD and -CD) (B), resorcin[4]arenes (C), and resorcin[4]arene-cavitands (D).

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