Rhodium catalysed hydroformlyation of higher alkenes using amphiphilic ligands: part 2

Buhling, Armin; Kamer, Paul C. J.; Leeuwen, Piet W. N. M. van; Elgersma, Jaap W.

doi:10.1016/s1381-1169(96)00195-1

Cited by 38 publications

(27 citation statements)

References 40 publications

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“…(19)) und deren Ablauf ^P j'H j-N M R -spektroskopisch verfolgt. Zu Ver gleichszwecken wurden die Phosphane Ph7P-C6H4-2-COOH (A) [2] und Ph2P-C6H4-3-P 02Na2 (A') [3] in die Untersuchungen einbezogen, um den Ef fekt der CH2-Spacergruppierung auf die katalyti sche Aktivität aufzuzeigen. Der Katalysator wurde separat durch Zugabe von acht Äquivalenten der je weiligen Phosphanliganden zu Palladium(II)-acetat in Ethylenglykol gebildet.…”

Section: Suzuki-kupplungsreaktionen Im Zweiphasensystemunclassified

“…A [2], B [3]) sind als Katalysatorliganden für die Hydrofor mylierung und Oligomerisation von Olefinen [4] sowie die Carbonylierung von Benzylhalogeni den in Zweiphasensystemen [3] von Bedeutung. Durch Immobilisierung aromatischer Phosphane mit P (0 )(0 R )2-Resten (B) an anorganischen Ma terialien (Zirconium(IV)-phosphat, -phosphonat, -phosphit) wurden geträgerte Katalysatoren erhal ten, die für Hydroformylierungs-und Heck-Reaktionen in heterogenen Systemen mit Erfolg einge setzt wurden [5,6].…”

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Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

Liek

Machnitzki

Nickel

et al. 1999

Zeitschrift Für Naturforschung B

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Nucleophilic phosphanylation of orf/zo-fluorophenylacetic acid or orf/jofluorobenzylamine with PhPH2 using KOfBu as the base affords the hydrophilic tertiary phosphanes 3 and 4a with terminal CH2-COOH and CH2-NH2 substituents. The corresponding secondary phosphane li gands 2 or 5 may be obtained by Pd-catalyzed P-C coupling of orr/20-iodophenylacetic acid with PhPH2 or selective nucleophilic phosphanylation of orf/jo-fluorophenylacetic acid. Novel phosphonatomethyl derivatives 7a, 7b of triphenylphosphane have been obtained in a two sta ge synthesis using orf/zo-iodobenzylchloride or w^ta-iodobenzylbromide as starting materials. Arbusov reaction with P(OEt)3 and Pd-catalyzed P-C coupling reactions with Ph2PH gave the esters 7a, 7b. Purification of 7a was achieved via its BH3 adduct 8a. Deprotection, hydrolysis and neutralisation with NaOH affords the water soluble sodium salts 9a,9b. a-Hydroxy and a-benzylamino derivatives 12 and 14 of orr/zo-diphenylphosphanobenzyl phosphonate (e.g. 7a) and the corresponding Me2P (0) analogs 13 and 16 are accessible in a straightforward man ner by addition of (M e0)2P(0)H or Me2P(0)H to orf/?o-phosphanobenzaldehyde 11a or its benzaldimino derivative 15, respectively. An improved synthesis for lla -llc has been develo ped. Reaction of 11a with the Wittig reagent Ph3P=C(H)COOEt and subsequent hydrolysis of the intermediate ester 17a affords o/t/?o-diphenylphosphano cinnamic acid 17. The catalytical activity of 1,9a, 9b and related ligands in Suzuki-type coupling reactions has been investigated. Derivate des Triphenylphosphans mit COOHund P (0 )(0 R )2-Gruppen (z.B. A [2], B [3]) sind als Katalysatorliganden für die Hydrofor mylierung und Oligomerisation von Olefinen [4] sowie die Carbonylierung von Benzylhalogeni den in Zweiphasensystemen [3] von Bedeutung. Durch Immobilisierung aromatischer Phosphane mit P (0 )(0 R )2-Resten (B) an anorganischen Ma terialien (Zirconium(IV)-phosphat, -phosphonat, -phosphit) wurden geträgerte Katalysatoren erhal ten, die für Hydroformylierungs-und Heck-Reaktionen in heterogenen Systemen mit Erfolg einge setzt wurden [5, 6]. Die Einschiebung einer CH(Z)-Brücke in A und B führt zu Liganden C bzw. D mit flexibler

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Section: Suzuki-kupplungsreaktionen Im Zweiphasensystemunclassified

unclassified

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

Liek

Machnitzki

Nickel

et al. 1999

Zeitschrift Für Naturforschung B

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“…30 Since then hydroformylation has been studied extensively using a variety of xantphos derivatives. 25,32,34,[60][61][62]64,114,116,[190][191][192][193][194][195][196][197][198][199][200][201][202][203][204] Given the importance of the oxidative addition of molecular hydrogen for both hydrogenation and hydroformylation, and to investigate any possible differences of the wide bite-angle and steric bulk of the t-Bu-xantphos ligands we investigated the reactivity of the [Rh(t-Bu-xantphos-κP,O,P ')Cl] complexes with dihydrogen.…”

Section: Reaction With Hydrogenmentioning

confidence: 99%

“…Platinum complexes are frequently synthesised as models for the analogous palladium species as they are frequently more stable, and the presence of 195 Pt allows for additional information in the NMR spectra, which can be useful in characterisation. However, palladium complexes are of particular interest due to their use in a wide range of catalytic processes.…”

Section: Reactions With Palladium(0) Precursorsmentioning

confidence: 99%

“…However, platinum complexes are typically more inert than their corresponding palladium analogues to processes such as ligand exchange and redox changes. 280 The presence of a spin active isotope 195 Pt (34% abundant) can result in coupling in the NMR spectra, which can give additional information about the nature of the complexes. This makes platinum a useful model for the chemistry of palladium.…”

Section: Chapter 6 Coordination Complexes With Platinum(ii) and Palladium(ii)mentioning

confidence: 99%

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Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

Nelson¹

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<p>This thesis provides an account of research into a group of diphosphine ligands with a rigid xanthene backbone and tert -butyl substituents on the phosphorus atoms. The three ligands have different groups in the bridgehead position of the backbone (CMe₂, SiMe₂, or S) which change the natural (calculated) bite-angle of the ligand. The coordination chemistry of these t -Bu-xantphos ligands with late-transition metals has been investigated with a focus on metal complexes that may form in catalytic reactions. The three t -Bu-xantphos ligands were synthesised by lithiation of the backbone using sec -butyllithium/TMEDA and treatment with PtBu₂Cl. The natural biteangles of the Ph-xantphos (111.89–114.18°) and t -Bu-xantphos (126.80–127.56°) ligands were calculated using DFT. The bite-angle of the t -Bu-xantphos ligands is larger due to the increased steric bulk of the tert -butyl substituents. The electronic properties of the t -Bu-xantphos ligandswere also investigated by synthesis of their phosphine selenides. The values of ¹J PSe (689.1–698.5Hz) indicate that the t -Bu-xantphos ligands have a higher basicity than Ph-xantphos between PPh₂Me and PMe₃. The silver complexes, [Ag(t -Bu-xantphos)Cl] and [Ag(t -Bu-xantphos)]BF₄ were synthesised with the t -Bu-xantphos ligands. In contrast to systems with phenyl phosphines, all species were monomeric. [Rh(t -Bu-xantphos)Cl] complexes were synthesised, which reacted with H₂, forming [Rh(t -Bu-xantphos-ĸP,O,P ’)Cl(H)₂] complexes, and with CO, forming [Rh(t -Bu-xantphos)(CO)₂Cl] complexes. The [Rh(t -Bu-xantphos)Cl] species are air-sensitive readily forming [Rh(t -Bu-xantphos)Cl(ƞ²-O₂)] complexes. The crystal structure of [Rh(t -Bu-xantphos)Cl(ƞ²-O₂)], contained 15% of the dioxygen sites replaced with an oxo ligand. This is the first crystallographic evidence of a rhodium(III) oxo complex, and only the third rhodium oxo species reported. The coordination chemistry of the ligands with platinum(0) and palladium(0) showed some differences. [Pt(t -Bu-xantphos)(C₂H₄)] complexes were synthesised for all three ligands. However, reaction with [Pt(nb)₃] produced a mixture of [Pt(t -Bu-xantphos)] and [Pt(t -Bu-xantphos)(nb)] for t -Bu-sixantphos and t -Buthixantphos. Although few examples of isolable [Pt(PP)] complexes with diphosphines have been reported [Pt(t -Bu-thixantphos)] was isolated by removal of the norbornene. t -Bu-Xantphos formed small amounts of [Pt(t -Bu-xantphos)] initially, which progressed to [Pt(t -Bu-xantphos)H]X. The analogous reactions with [Pd(nb)₃] gave [Pd(t -Bu-xantphos)] and [Pd(t -Bu-xantphos)(nb)] complexes in all cases. [Pt(t -Bu-thixantphos)(C₂H₄)] and [M(t -Bu-thixantphos)] (M = Pd, Pt) react with oxygen forming [Pt(t -Bu-thixantphos)(ƞ²-O₂)], which reacts with CO to give [Pt(t -Bu-thixantphos-H-ĸ-C,P,P ’)OH] through a series of intermediates. [M(t -Bu-xantphos)Cl₂] (M = Pd, Pt) complexes were synthesised, showing exclusive trans coordination of the diphosphine ligands. The X-ray crystal structure of [Pt(t -Bu-thixantphos)Cl₂] has a bite-angle of 151.722(15)°. This is the first [PtCl₂(PP)] complex with a bite-angle between 114 and 171°. In polar solvents a chloride ligand dissociates from the [Pt(t -Bu-xantphos)Cl₂] complexes producing [Pt(t -Bu-xantphos-ĸP,O,P ’)Cl]⁺. The analogous [Pd(t -Bu-xantphos-ĸP,O,P ’)Cl]⁺ complexes were formed by reaction of the dichlorides complexes with NH₄PF₆. The [Pt(t -Bu-xantphos-ĸP,O,P ’)Me]⁺ pincer complexes were the only product from reaction with [Pt(C₆H₁₀)ClMe], with the stronger trans influence of the methyl ligand promoting loss of the chloride. The formation of the pincer complexes was further explored using DFT. The values of J PtC for the methyl carbons in the [Pt(t -Bu-xantphos-ĸP,O,P ’)Me]⁺ complexes, and J RhH for the hydride trans to the oxygen atom in the [Rh(t -Buxantphos-ĸP,O,P ’)Cl(H)₂] complexes were largest for t -Bu-sixantphos, then t -Buthixantphos, then t -Bu-xantphos. The trans influence of the t -Bu-xantphos oxygen donor follows the trend t -Bu-sixantphos < t -Bu-thixantphos < t -Bu-xantphos.</p>

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Water as a Reaction Solvent – an Industry Perspective

Wiebus¹,

Cornils²

2007

Organic Reactions in Water

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Rhodium catalysed hydroformlyation of higher alkenes using amphiphilic ligands: part 2

Cited by 38 publications

References 40 publications

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

Water as a Reaction Solvent – an Industry Perspective

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Rhodium catalysed hydroformlyation of higher alkenes using amphiphilic ligands: part 2

Cited by 38 publications

References 40 publications

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH2-, COOH- und P(O)(OR)2-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH2, COOH and P (O)(OR)2 Functionalized Side Chains

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH2-, COOH- und P(O)(OR)2-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH2, COOH and P (O)(OR)2 Functionalized Side Chains

Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

Water as a Reaction Solvent – an Industry Perspective

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Product

Resources

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Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains