High‐Pressure 31P{1H} NMR Studies of RhH(CO)(TPPTS)3 in the Presence of Methylated Cyclodextrins: New Light on Rhodium‐Catalyzed Hydroformylation Reaction Assisted by Cyclodextrins

Monflier, Éric; Bricout, H.; Hapiot, F.; Tilloy, S.; Aghmiz, Ali; Masdeu‐Bultó, Anna M.

doi:10.1002/adsc.200303182

Cited by 59 publications

(50 citation statements)

References 46 publications

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“…In particular, the aldehydes selectivity and the linear to branched ratio (l/b ratio) of aldehyde products are indicative of the nature of the catalytic species and of interactions between the CD and the phosphane, respectively. [6] Indeed, we have demonstrated that the l/b ratio decrease observed in the presence of RAME-b-CD (1.8 vs. 2.8 without CD) was due to trapping of the phosphane ligand by CD and it is suspected that the high aldehydes selectivity (97% vs. 59% without CD) is due to an interaction between the CD and the catalytic rhodium species during coordination of the olefin on the metal center.…”

Section: Resultsmentioning

confidence: 96%

“…[10] Second, as it has been demonstrated that inclusions between RAME-b-CD and phosphanes greatly affected the performance of catalytic systems, [6,7] an NMR study has been performed to provide information about the ability of KSPDM-b-CD to interact with hydrosoluble phosphane ligands. Two phosphanes widely used in aqueous organometallic catalysis have been chosen for this study: the sodium salt of the meta-substituted trisulfonated triphenylphosphine (TPPTS) and the sodium salt of the meta-substituted monosulfonated triphenylphosphine (TPPMS).…”

Section: Resultsmentioning

confidence: 99%

“…Indeed, RAME-b-CD can form inclusion complexes with the hydrosoluble phosphane ligands used to dissolve the transition metal in the aqueous phase. [5] These inclusion complexes were responsible for the decrease in the linear to branched aldehydes ratio during the rhodium-catalyzed hydroformylation reaction [6] and a drop in cyclodextrin activity in some experimental conditions. [7] Consequently, there is a real interest to find cyclodextrins that do not interact with the ligands or the organometallic catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin: A Genuine Supramolecular Carrier for Aqueous Organometallic Catalysis

et al. 2006

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The behavior of heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-b-cyclodextrin as inverse phase transfer catalyst in biphasic Tsuji-Trost and hydroformylation reactions has been investigated. In terms of activity, this methylated sulfopropyl ether b-cyclodextrin is much more efficient than the randomly methylated b-cyclodextrin, which was the most active cyclodextrin known to date. From a selectivity point of view, the intrinsic properties of the catalytic system are fully preserved in the presence of this cyclodextrin as the chemo-or regioselectivity was found to be identical to that observed without a mass transfer promoter in the hydroformylation reaction. The efficiency of this cyclodextrin was attributed to its high surface activity and to the absence of interactions with the catalytically active species and the water-soluble phosphane used to dissolve the organometallic catalyst in the aqueous phase.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin: A Genuine Supramolecular Carrier for Aqueous Organometallic Catalysis

et al. 2006

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“…[6] The formation of such inclusion complexes induces a decrease in the linear to branched aldehyde ratio during the rhodium-catalyzed hydroformylation reaction. [7] In fact, the Rame-b-CD is able to dissociate TPPTS from the rhodium species and leads to the formation of low-coordinated phosphane species responsible for this decrease in regioselectivity. In addition, it has been shown that the ability of Rame-b-CD to bind to the TPPTS ligand can contribute to decrease the reaction rates.…”

Section: Introductionmentioning

confidence: 99%

Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins: How to Design the Water‐Soluble Phenylphosphane to Avoid Interaction with Cyclodextrin

et al. 2008

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The ability of cyclodextrin to interact with meta-trisulfonated triphenylphosphane derivatives bearing one or two methyl (or methoxy) groups on the aromatic ring has been investigated by NMR and UV-vis spectroscopy. In the case of native b-cyclodextrin (b-CD), the presence of one methyl or methoxy group in the ortho-position on each aromatic ring is necessary to hamper the formation of an inclusion complex between the b-CD and meta-trisulfonated triphenylphosphane derivatives. In the case of methylated b-CD, the formation of an inclusion complex is only observed when the meta-trisulfonated triphenylphosphane contains a methyl group in the para-position. The poor affinity of methylated b-CD towards modified trisulfonated triphenylphosphanes was attributed to the steric hindrance generated by the methyl groups on the CD secondary face. The absence or presence of an interaction between phosphanes and methylated b-CD was also confirmed by catalytic experiments. Thus, the phosphanes that do not interact with the methylated CD were the most efficient mass-transfer promoters in an aqueous biphasic palladium-catalyzed Tsuji-Trost reaction.

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“…[6] In this context, it was of great interest to evaluate in a cyclodextrin-based hydrofomylation process the behavior of rhodium complexes associated to the highly water-soluble ligand m-TPPTC [tris(m-carboxyphenyl) phosphane trilithium salt] (Scheme 1), a carboxylated analogue of the sulfonated TPPTS ligand.…”

Section: Introductionmentioning

confidence: 99%

Water‐Soluble Triphenylphosphane‐3,3′,3′′‐tricarboxylate (m‐TPPTC) Ligand and Methylated Cyclodextrins: A New Combination for Biphasic Rhodium‐Catalyzed Hydroformylation of Higher Olefins

et al. 2006

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Abstract:The methylated cyclodextrins/m-TPPTC [tris(m-carboxyphenyl)phosphane trilithium salt] couples proved to be more efficient than the wellknown methylated cyclodextrins/TPPTS [tris(m-sulfonatophenyl)phosphane trisodium salt] systems in terms of activities and selectivities to perform the Rh-catalyzed hydroformylation of higher olefins in an aqueous-organic system. The interactions cyclodextrins/m-TPPTC have been fully studied by NMR spectroscopy.Keywords: cyclodextrin; hydroformylation; phosphane; rhodium; water-soluble ligand Rhodium-catalyzed hydroformylation in an aqueousorganic two-phase system appears to be an economical and safe approach.[1] Indeed, an aqueous biphasic system allows quantitative recycling of the catalyst and decreases harmful emissions and costs associated with solvent recycling. Unfortunately, the industrial viability of the biphasic hydroformylation process has only been demonstrated in the case of lower olefins such as propene and butene with a Rh/TPPTS [TPPTS = tris(m-sulfonatophenyl)phosphane trisodium salt] catalytic system.[2] In the case of higher olefins (five or more carbon atoms), the olefin solubility is too low for industrially important rates to be achieved and the presence of a mass transfer promoter is required.[3] Among the different approaches proposed to increase the solubility of higher olefins, the use of chemically modified b-cyclodextrins such as methylated cyclodextrins preserves some economical viability.[4] Indeed, the methylated cyclodextrins that are cheap, non-toxic and bulk commercially available compound allowed us to achieve the hydroformylation of higher olefins with high reaction rate and chemoselectivity, while avoiding the formation of an emulsion and the partition of the rhodium catalyst between the organic and aqueous phases.[5] However, it was found that the regioselectivity, i.e., the linear to branched aldehydes ratio can be decreased due to interaction between the TPPTS ligand and the cyclodextrin. [6] In this context, it was of great interest to evaluate in a cyclodextrin-based hydrofomylation process the behavior of rhodium complexes associated to the highly water-soluble ligand m-TPPTC [tris(m-carboxyphenyl) phosphane trilithium salt] (Scheme 1), a carboxylated analogue of the sulfonated TPPTS ligand.[7] Actually, while m-TPPTC has been widely used in organometallic reactions, [8] its performances have never been described in the hydroformylation of olefins and the behavior of this phosphane ligand towards CDs has never been investigated. We describe herein our preliminary results concerning the m-TPPTC/CDs couple and the catalytic activity of the rhodium/m-TPPTC system in the hydroformylation of 1-octene, 1-decene and 1-dodecene.The interaction between m-TPPTC and native or randomly methylated a-cyclodextrin or b-cyclodextrin (Scheme 1) has been studied by NMR spectroscopy. First, as no chemical shift was detected on the

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High‐Pressure ³¹P{¹H} NMR Studies of RhH(CO)(TPPTS)₃ in the Presence of Methylated Cyclodextrins: New Light on Rhodium‐Catalyzed Hydroformylation Reaction Assisted by Cyclodextrins

Cited by 59 publications

References 46 publications

Heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin: A Genuine Supramolecular Carrier for Aqueous Organometallic Catalysis

Heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin: A Genuine Supramolecular Carrier for Aqueous Organometallic Catalysis

Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins: How to Design the Water‐Soluble Phenylphosphane to Avoid Interaction with Cyclodextrin

Water‐Soluble Triphenylphosphane‐3,3′,3′′‐tricarboxylate (m‐TPPTC) Ligand and Methylated Cyclodextrins: A New Combination for Biphasic Rhodium‐Catalyzed Hydroformylation of Higher Olefins

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