Rhodium catalysed methanol carbonylation in the presence of bis(ditertiarybutylphosphinomethyl)benzene

Jiménez-Rodríguez, Cristina; Pogorzelec, Peter J.; Eastham, Graham R.; Slawin, Alexandra M. Z.; Cole‐Hamilton, David J.

doi:10.1039/b701582h

Cited by 25 publications

(14 citation statements)

References 19 publications

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“…The 31 P NMR spectrum (CDCl 3 , see Supporting Information Figure S20) of [(BPX)Rh(CO)Cl] consisted of two doublets of doublets at 51.5 ppm ( 1 J Rh−P = 173.7 Hz, 2 J P−P = 32.6 Hz, trans to Cl) and 13.9 ppm ( 1 J Rh−P = 127.0 Hz, 2 J P−P = 32.1 Hz, trans to CO), which is similar to the 31 P NMR spectrum of [(DTBPX)Rh-(CO)Cl], although in the latter case the respective one-bond Rh−P coupling constants are slightly smaller at 170.8 and 123.2 Hz, respectively. 32 Previous studies have shown correlations between the magnitude of the one-bond Rh−P coupling constants and the σ-donation of the trans influencing ligand. 33 It is thought that coupling constants of a given metal and ligand are a good indicator of the relative s characters of the orbitals involved.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst

et al. 2016

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The synthesis and characterization of bulky diphosphine 1,2-bis(4-phosphorinone)xylene, BPX, and its palladium complexes [(BPX)PdCl 2 ] and [(BPX)Pd(O 2 CCF 3 ) 2 ] are described. BPX was evaluated as a ligand in Pd-catalyzed isomerizing methoxycarbonylation. A broad range of alkenes, including terminal, internal, branched, and functionalized alkenes, can be converted to esters with activities and selectivities matching or surpassing the performance of the state-of-the-art palladium bis(di(tert-butyl)phosphino-o-xylene (Pd-DTBPX) catalyst. A molecular structure of the precatalyst [(BPX)Pd(O 2 CCF 3 ) 2 ] was obtained showing a square planar geometry and a bite angle of 100.11(3)°. Rhodium carbonyl complexes [(BPX)Rh(CO)Cl] and [(DTBPX)Rh(CO)Cl] were synthesized to compare the relative electronic parameters, revealing a ν(CO) of 1956.8 and 1948.3 cm −1 , respectively, suggesting a reduced ability of BPX to donate electron density to the metal relative to DTBPX. Competitive protonation experiments between BPX and DTBPX in the presence of CH 3 SO 3 H exclusively produce [DTBPX(H) 2 ] 2+ , providing additional evidence that BPX is a much weaker base than DTBPX. This could be due to either the effect of the electron-withdrawing ketone group in the phosphorinone ring or the compression of the C−P−C bond angle induced by the ring structure. The 31 P NMR (CDCl 3 ) chemical shift of BPX is 5.6 ppm, upfield of DTBPX at 27.6 ppm. This anomalous result is attributed to a strong gamma substituent effect of CO in the BPX ligand. The improved activity of Pd-BPX, relative to Pd-DTBPX, could be attributed to a more electrophilic Pd II center, which could accelerate the rate-determining methanolysis step.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst

et al. 2016

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“…Another prominent approach to achieve an isomerizing functionalization is isomerizing alkoxycarbonylation. 142,143 This reaction, first observed for fatty acid esters by Cole-Hamilton and co-workers, 144 converts the internal double bond deep in the hydrocarbon chain very selectively to a terminal ester group by reaction with carbon monoxide and methanol. The reaction is promoted by Pd(II) catalysts with bulky electron-rich diphosphine ligands, like 1,2-bis[(di-tert-butylphosphino)methyl]benzene (dtbpx).…”

Section: Isomerization Functionalizationmentioning

confidence: 99%

Long-Chain Aliphatic Polymers To Bridge the Gap between Semicrystalline Polyolefins and Traditional Polycondensates

2016

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Other than their established short-chain congeners, polycondensates based on long-chain difunctional monomers are often dominated by the long methylene sequences of the repeat units in their solid-state structures and properties. This places them between traditional polycondensates and polyethylenes. The availability of long-chain monomers as a key prerequisite has benefited much from advances in the catalytic conversion of plant oils, via biotechnological and purely chemical approaches, likewise. This has promoted studies of, among others, applications-relevant properties. A comprehensive account is given of long-chain monomer syntheses and the preparation and physical properties, morphologies, mechanical behavior, and degradability of long-chain polyester, polyamides, polyurethanes, polyureas, polyacetals, and polycarbonates.

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“…171 The process of methanol carbonylation is traditionally carried out with cis-[Rh(CO) 2 I 2 ] -in the Monsanto process. 102 The authors showed that a catalytic system based on [RhCl(CO) 2 ] 2 /DTBPMB, with added methyl iodide, gives higher initial rates for the reaction than the Monsanto catalyst at 150-180℃.…”

Section: Other Reactions Involving Rhodiummentioning

confidence: 99%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

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Dimethyl 1,19-nonadecanedioate is produced from the methoxycarbonylation of commercial olive, rapeseed or sunflower oils in the presence of a catalyst derived from [Pd 2 (dba) 3 ], bis(ditertiarybutylphosphinomethyl)benzene (BDTBPMB) and methanesulphonic acid (MSA). The diester is then hydrogenated to 1,19-nonadecanediol using Ru/1,1,1-tris-(diphenylphosphinemethyl)ethane (triphos). 1,19-Nonadecadienoic acid is hydrogenated to short chain oligoesters, which can themselves be hydrogenated to 1,19-nonadecanol by hydrogenation in the presence of water.

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Rhodium catalysed methanol carbonylation in the presence of bis(ditertiarybutylphosphinomethyl)benzene

Cited by 25 publications

References 19 publications

Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst

Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst

Long-Chain Aliphatic Polymers To Bridge the Gap between Semicrystalline Polyolefins and Traditional Polycondensates

Polymer precursors from catalytic reactions of natural oils

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