A protein–rhodium complex as an efficient catalyst for two-phase olefin hydroformylation

Marchetti, Mauro; Mangano, Giuseppe Donato; Paganelli, Stefano; Botteghi, C.

doi:10.1016/s0040-4039(00)00473-1

Cited by 62 publications

(38 citation statements)

References 16 publications

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“…In the last years natural compounds, such as aminoacids, peptides, proteins and sugars have been used as ligands for metallic species active as catalysts [5][6][7][8][9]. In this context, some years ago we reported highly efficient and chemoselective hydroformylation [10][11][12] and hydrogenation [8] reactions using water-soluble complexes derived from the interaction between Rh(CO) 2 (acac) or [Ir(COD)Cl] 2 , respectively, with human serum albumin (HSA). Previous studies, carried out by us on the catalytic system Rh/HSA, showed an outstanding correspondence between the surface distribution of Rh and S atoms of the protein, therefore we hypothesized that the metal atom mainly interacts with the sulphur atoms [13,14]: the great affinity of "soft" metals, such as rhodium, for the thiolic group is well known [15].…”

Section: Introductionmentioning

confidence: 99%

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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a b s t r a c tRh(DHTANa) is a new water-soluble catalyst easily obtained by mixing in water the catalytic precursor [Rh(COD)Cl] 2 and the dihydrothioctic acid sodium salt (DHTANa). This catalyst showed to be very active in the hydrogenation of unsaturated substrates as 2-cyclohexen-1-one, the biomass-derived furfural and acetophenone. In this last case the catalytic system obtained by using as water-soluble ligand (R)-(DHTANa) afforded (R)-1-phenylethanol with very modest enantioselectivity. Rh(DHTANa) was active also in the aqueous biphase hydroformylation of styrene producing exclusively the two corresponding aldehydes with 80-86% selectivity toward the branched aldehyde 2-phenylpropanal. This new catalytic system was easily recycled in both hydrogenation and hydroformylation processes and no leaching phenomenon was observed.

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Section: Introductionmentioning

confidence: 99%

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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“…1 H-NMR signals of the benzothiazole rings generally shift to a slightly lower field upon coordination, and slight upfield or downfield shifts in the d values are observed in the 13 C-NMR spectra for compounds 3 ± 6. 13 C-nMR-Shift changes do not necessarily reflect local charge changes as the paramagnetic component of the chemical shift significantly contributes to the total chemical shift, unlike the chemical shift in 1 H-NMR spectra, which is totally determined by the diamagnetic contribution of the chemical shift and, thus, directly reflects local charge movement [16].…”

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confidence: 97%

“…± Our interest in rhodium complexes that contain ligands similar to compounds in biological systems has been raised since the successful use of rhodium complexes with H 2 O-soluble biopolymers (human-serum albumin) as ligands in the hydroformylation of olefins [1]. Several groups have described the synthesis, characterization, and application of rhodium(I) complexes containing five-membered heterocycles in homogeneous catalytic transformations [2 ± 11].…”

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confidence: 99%

New Rhodium Complexes Coordinated by Bidentate Imine Ligands with Benzothiazolyl Functionalities

Julius

Cronje

Neveling

et al. 2002

HCA

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Dedicated to Professor Dieter Seebach on the occasion of his 65th birthdayThe pseudo-square-planar complexes [Rh(cod)(Hbbtm)]BF 4 (3), [Rh(bbte)(cod)]BF 4 (4), [Rh(CO) 2 (Hbbtm)]BF 4 (5), [Rh(bbte)(CO) 2 ]BF 4 (6), [Rh(bbtm)(cod)] (7) and [Rh(bbtm)(CO) 2 ] (8) (Hbbtm bis(benzothiazol-2-yl)methane 2,2'-methylenebis[benzothiazole], bbte bis(benzothiazol-2-yl)ethane 2,2'-(ethane-1,2-diyl)bis[benzothiazole], and cod cycloocta-1,5-diene) were synthesized and characterized. Diastereotopic protons were observed for the protons at the bridge in the 1 H-NMR of 3 and 5. Twisting of the ethane-1,2-diyl bridge in 4 and 6 effects chemical equivalence of the CH 2 groups in solution. Unusually large downfield shifts occur on coordination of the deprotonated ligand Hbbtm as the negative charge is delocalized in 7 and 8. The NMR signals of the cod ligand in 4 could be differentiated. The X-ray crystal structures of 3, 4, and 6 are reported.Introduction. ± Our interest in rhodium complexes that contain ligands similar to compounds in biological systems has been raised since the successful use of rhodium complexes with H 2 O-soluble biopolymers (human-serum albumin) as ligands in the hydroformylation of olefins [1]. Several groups have described the synthesis, characterization, and application of rhodium(I) complexes containing five-membered heterocycles in homogeneous catalytic transformations [2 ± 11].[Rh(CH 2 {mBnzim} 2 )(CO) 2 ]BPh 4 and [Rh(CH 2 {mim} 2 )(CO) 2 ]BPh 4 (mBnzim methylbenzimidazolyl and mim methylimidazolyl) have been structurally characterized [2] and used in the intramolecular hydroamination of terminal and nonterminal alkynes [3] and the cyclization of acetylenic carboxylic acids and acetylenic alcohols to afford O-containing heterocycles [4]. The methylene-bridge protons undergo exchange in deuterated solvents once the ligand is coordinated to the metal center. Accordingly, deprotonation of Hbbom (bis(2-benzoxazol-2-yl)methane) and reaction with [RhCl(CO) 2 ] 2 yielded [Rh(bbom)(CO) 2 ], but this complex proved to be a weak catalyst precursor for the reduction of nitrobenzene to aniline [5].Oro and co-workers [6] have described the synthesis and structural characterization of mononuclear and binuclear rhodium(I) complexes with the general formulae [{RhCl(CH 2 (pz) 2 )(cod)} 2 ], [Rh(CH 2 (pz) 2 )(cod)]ClO 4 and [Rh(CH 2 (pz) 2 )(CO) 2 ]ClO 4 (CH 2 (pz) 2 bis(pyrazolyl)methane). Hydroformylation of hex-1-ene and heptenes are catalysed by [Rh 2 (CO) 2 {P(OPh) 3 } 2 (m-pz) 2 ] [7] and [Rh{P(OPh) 3 } 2 (pz)] 2 [8] (pz pyrazolato) under mild conditions. Evidence that binuclear [Rh 2 Cl 2 (cod) 2 (L)] complexes that contain bidentate NN' and tridentate NN'N 1-(alkylamino)pyrazoles exist as ionic species was recently presented [10]. Substitution of a CO ligand in

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“…[1][2][3][4] and also natural compounds, such as aminoacids, peptides, proteins and sugars have been used as ligands in combination with transition metal species in order to obtain catalysts active in water [9][10][11][12][13][14][15][16][17][18]. For some time now, our research group has been involved in the synthesis of triazolyl ligands taking advantage of the coppercatalyzed azide-alkyne [3+2] cyclization (Scheme 1) [19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

A pyridyl-triazole ligand for ruthenium and iridium catalyzed CC and CO hydrogenations in water/organic solvent biphasic systems

Paganelli

Alam

Beghetto

et al. 2015

Applied Catalysis A: General

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a b s t r a c tThe water soluble pyridyl-triazole ligand sodium 2-(1-((pyridin-2-yl)methyl)-1H-1,2,3-triazol-4-yl) ethyl sulfate (Na1) has been successfully employed in combination with ruthenium and iridium for catalytic hydrogenation of C C and C O double bonds in water/toluene biphasic systems. Reaction of the ligand with [RuCl 2 ( 6 -p-cymene)] 2 affords the new water soluble complex [RuCl( 6 -p-cymene)(1)] (2) which has been found to be catalytically active in the water/organic solvent biphasic hydrogenation using styrene and 2-cyclohexen-1-one as model substrates. Very conveniently, the iridium based catalytic system is prepared by simply stirring in water [Ir( 4 -COD)Cl] 2 with Na1 (Ir:Na1 molar ratio = 1:4), the resulting solution is catalytically active and appears more efficient than 2. With both the Ru-and Ir-based systems the catalytically active aqueous phases can be used at least three times without loss of activity.

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A protein–rhodium complex as an efficient catalyst for two-phase olefin hydroformylation

Cited by 62 publications

References 16 publications

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

New Rhodium Complexes Coordinated by Bidentate Imine Ligands with Benzothiazolyl Functionalities

A pyridyl-triazole ligand for ruthenium and iridium catalyzed CC and CO hydrogenations in water/organic solvent biphasic systems

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