Synthesis of new calix[4]arene‐based phosphorus ligands and their application in the Rh(I) catalyzed hydroformylation of 1‐octene

Kunze, Christine; Selent, Detlef; Neda, Ion; Schmutzler, Reinhard; Spannenberg, Anke; Börner, Armin

doi:10.1002/hc.1088

Cited by 43 publications

(31 citation statements)

References 32 publications

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“…A similar l:b decrease has already been observed by Bçrner et al with other phosphorus-containing calixarenes. [25] The reason for the selectivity decrease with 12 remains unclear. Possibly ligand 12 displays a weaker chelating power and therefore decoordinates gradually, hence leading to a less selective catalyst.…”

Section: Catalyticmentioning

confidence: 99%

Highly Regioselective Hydroformylation with Hemispherical Chelators

Sémeril

Matt

Toupet

2008

Chemistry A European J

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The hemispherical diphosphites (R,R)- or (S,S)-5,11,17,23-tetra-tert-butyl-25,27-di(OR)-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix[4]arene (R=OPr, OCH(2)Ph, OCH(2)-naphtyl, O-fluorenyl; R=H, R'=OPr) (L(R)), all with C(2) symmetry, have been synthesised starting from the appropriate di-O-alkylated calix[4]arene precursor. In the presence of [Rh(acac)(CO)(2)], these ligands straightforwardly provide chelate complexes in which the metal centre sits in a molecular pocket defined by two naphthyl planes related by the C(2) axis and the two apically situated R groups. Hydroformylation of octene with the L(Pr)/Rh system turned out to be highly regioselective, the linear-to-branched (l:b) aldehyde ratio reaching 58:1. The l:b ratio significantly increased when the propyl groups were replaced by -CH(2)Ph (l:b=80) or -CH(2)naphthyl (l:b=100) groups, that is, with substituents able to sterically interact with the apical metal sites, but without inducing an opening of the cleft nesting the catalytic centre. The trend to preferentially form the aldehyde the shape of which fits with the shape of the catalytic pocket was further confirmed in the hydroformylation of styrene, for which, in contrast to catalysis with conventional diphosphanes, the linear aldehyde was the major product (up to ca. 75 % linear aldehyde). In the hydroformylation of trans-2-octene with the L(benzyl)/Rh system, combined isomerisation/hydroformylation led to a remarkably high l:b aldehyde ratios of 25, thus showing that isomerisation is more effective than hydroformylation. Unusually large amounts of linear products were also observed with all the above diphosphites in the tandem hydroformylation/amination of styrene (l:b of ca. 3:1) as well as in the hydroformylation of allyl benzyl ether (l:b ratio up to 20).

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Section: Catalyticmentioning

confidence: 99%

Highly Regioselective Hydroformylation with Hemispherical Chelators

Sémeril

Matt

Toupet

2008

Chemistry A European J

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“…It is noteworthy that the selectivities towards linear aldehydes were considerably superior to those ob- tained with related diphosphites having smaller P-substituents. [24,25] Recently, we showed that these neutral complexes may also be used in aqueous medium, provided a sulfonated calix [4]arene acting as surfactant is added to the reaction mixture. [26] No significant loss of regioselectivity was observed.…”

Section: Introductionmentioning

confidence: 99%

Solvent‐Free Olefin Hydroformylation Using Hemispherical Diphosphites

2010

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With rhodium complexes containing hemispherical diphosphite ligands derived from a calixarene skeleton, olefins can be hydroformylated efficiently under solvent‐free conditions. For example, in the hydroformylation of 1‐octene (T = 80 °C, P = 20 bar, olefin:Rh = 200 000:1) one of the catalysts investigated resulted in a TOF of 17290 mol (converted 1‐octene)·mol(Rh)–1·h–1, the regioselectivity towards the linear aldehyde reaching then 97.9 %.

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“…In this case the calixarene acts as a chelating ligand using its nearest phosphorus atoms, in contrast to 1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituted 4-tertbutyl-calix [4]arene, which complexes two Au-Cl units through the opposite phosphorus atoms farthest apart from each other [14]. The calixarene shows the cone conformation, as did the free calixarene previously reported (values for comparison in square brackets) [6]. The bridging carbon atoms are almost coplanar; C17 and C37 lie 2.9 pm on one side of the plane, C27 and C47 2.9 pm on the other [av.…”

Section: Single Crystal X-ray Structure Determination Ofmentioning

confidence: 77%

“…Thus, we have reported the synthesis of a wide variety of calix [4]arenes containing trivalent phosphorus groups and their application to the hydroformylation of 1-octene [6], although we did not know the exact nature of the catalysts formed in situ.…”

Section: Introductionmentioning

confidence: 99%

“…1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituted calix [4]arenes have been known for some years [11]. Recently, we reported the excellent chelating properties of these compounds with regard to complexation to rhodium and platinum [6,12]. In the present paper, we have investigated the synthesis of a number of new and interesting monomeric and dimeric complexes of these calix [4]arenes with rhodium and platinum.…”

Section: Introductionmentioning

confidence: 99%

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Mono- and Binuclear Rhodium and Platinum Complexes of 1, 3, 5-Trimethyl-1, 3, 5-triaza-2σ3λ3-phosphorin-4, 6-dionyloxy-substituted Calix[4]arenes

Kunze

Neda

Freytag

et al. 2002

Z. anorg. allg. Chem.

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The reaction behaviour of 1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituted calix[4]arenes towards mono-and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)-substituted calix[4]arene (4) and its tert-butyl-derivative (1) with [(cod)RhCl] 2 yielded the mono-and disubstituted binuclear rhodium complexes 2, 3, and 5. In all cases, a C 2 -symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1,3-alternating conformation. The X-ray crystal structure determination of 5 confirmed [(calixarene)RhCl] 2 -coordination through two opposite phosphorus atoms with a P····P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh 2 Cl 2 core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)-bis(methoxy)-substituted tert-butyl-calix-[4]arene (7) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF 4 led to the expected cationic monorhodium Ein-und zweikernige Komplexe des Rhodiums und Platins von 1,3,5-Trimethyl-1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituierten Calix[4]arenen Inhaltsübersicht. Das Reaktionsverhalten von 1,3,5-Trimethyl-1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituierten Calix-[4]arenen gegenüber ein-und zweikernigen Rhodium-und PlatinKomplexen wurde untersucht. Besonderes Augenmerk wurde auf die Untersuchung der Struktur und des dynamischen Verhaltens der Produkte im festen Zustand und in Lösung gelegt. Abhängig vom molaren Verhältnis der Reaktanden lieferte die Umsetzung des tetrakis(triazaphosphorindionyloxy)-substituierten Calix[4]-arens (4) und seines tert-Butyl-Analogons (1) mit [(cod)RhCl] 2 die mono-und disubstituierten, zweikernigen Rhodiumkomplexe 2, 3 und 5. In allen Fällen wurde eine C 2 -symmetrische Struktur in Lö-sung nachgewiesen, die anscheinend aus einem schnellen intramolekularen Austauschprozeß zwischen der Konus-und der 1,3-alternierenden Konformation resultiert. Die Röntgenstrukturana-lyse von 5 bestätigte die [(Calixaren)RhCl] 2 -Koordination über zwei gegenüberliegende Phosphoratome mit einem P····P-Abstand von 345 pm. Der Komplex zeigt kristallographische Inversionssymmetrie, damit ist die Rh 2 Cl 2 -Verbrückungseinheit exakt planar. Die Reaktion von 1 und dem bis(triazaphosphorindionyloxy)-bis(methoxy)-substituierten tert-Butyl-Calix[4]aren (7) mit (cod)-Rh(acac) in äquimolarem Verhältnis und anschließender Umsetcomplexes 6 and 8, involving 1,3-alternating P-Rh-P-coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the 1 J(PRh) coupling constants in the 31 P-NMR-spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after a...

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Synthesis of new calix[4]arene‐based phosphorus ligands and their application in the Rh(I) catalyzed hydroformylation of 1‐octene

Abstract: ABSTRACT:The synthesis of calix [4]

Cited by 43 publications

References 32 publications

Highly Regioselective Hydroformylation with Hemispherical Chelators

Highly Regioselective Hydroformylation with Hemispherical Chelators

Solvent‐Free Olefin Hydroformylation Using Hemispherical Diphosphites

Mono- and Binuclear Rhodium and Platinum Complexes of 1, 3, 5-Trimethyl-1, 3, 5-triaza-2σ3λ3-phosphorin-4, 6-dionyloxy-substituted Calix[4]arenes

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