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Author: Franke, Robert × Author: Spannenberg, Anke × DDC: 540 × Type: Text ×

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Now showing 1 - 4 of 4
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    Cooperative catalytic methoxycarbonylation of alkenes: Uncovering the role of palladium complexes with hemilabile ligands
    (Cambridge : RSC, 2018) Dong, Kaiwu; Sang, Rui; Wei, Zhihong; Liu, Jie; Dühren, Ricarda; Spannenberg, Anke; Jiao, Haijun; Neumann, Helfried; Jackstell, Ralf; Franke, Robert; Beller, Matthias
    Mechanistic studies of the catalyst [Pd2(dba)3/1,1′-bis(tert-butyl(pyridin-2-yl)phosphanyl)ferrocene, L2] for olefin alkoxycarbonylation reactions are described. X-ray crystallography reveals the coordination of the pyridyl nitrogen atom in L2 to the palladium center of the catalytic intermediates. DFT calculations on the elementary steps of the industrially relevant carbonylation of ethylene (the Lucite α-process) indicate that the protonated pyridyl moiety is formed immediately, which facilitates the formation of the active palladium hydride complex. The insertion of ethylene and CO into this intermediate leads to the corresponding palladium acyl species, which is kinetically reversible. Notably, this key species is stabilized by the hemilabile coordination of the pyridyl nitrogen atom in L2. The rate-determining alcoholysis of the acyl palladium complex is substantially facilitated by metal-ligand cooperation. Specifically, the deprotonation of the alcohol by the built-in base of the ligand allows a facile intramolecular nucleophilic attack on the acyl palladium species concertedly. Kinetic measurements support this mechanistic proposal and show that the rate of the carbonylation step is zero-order dependent on ethylene and CO. Comparing CH3OD and CH3OH as nucleophiles suggests the involvement of (de)protonation in the rate-determining step.
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    Synthesis of C2-Symmetric Diphosphormonoamidites and Their Use as Ligands in Rh-Catalyzed Hydroformylation: Relationships between Activity and Hydrolysis Stability
    (Weinheim : Wiley-VCH-Verl., 2017-1-23) Morales Torres, Galina; Behrens, Stephan; Michalik, Dirk; Selent, Detlef; Spannenberg, Anke; Lühr, Susan; Dyballa, Katrin Marie; Franke, Robert; Börner, Armin
    A series of diphosphoramidites has been synthetized with a piperazine, homopiperazine, and an acyclic 1,2-diamine unit in the backbone. New compounds were tested alongside related N-acyl phosphoramidites as ligands in the Rh-catalyzed hydroformylation of n-octenes to investigate their influence on the activity and regioselectivity. A subsequent study of their hydrolysis stability revealed that the most stable ligands induced the highest activity in the catalytic reaction.
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    Hydrolysis Stability of Bidentate Phosphites Utilized as Modifying Ligands in the Rh-Catalyzed n-Regioselective Hydroformylation of Olefins
    (Washington, DC : ACS, 2016) Zhang, Baoxin; Jiao, Haijun; Michalik, Dirk; Kloß, Svenja; Deter, Lisa Marie; Selent, Detlef; Spannenberg, Anke; Franke, Robert; Börner, Armin
    The stability of ligands and catalysts is an almost neglected issue in homogeneous catalysis, but it is crucial for successful application of this methodology in technical scale. We have studied the effect of water on phosphites, which are the most applied cocatalysts in the n-regioselective homogeneous Rh-catalyzed hydroformylation of olefins. The stability of the bidentate nonsymmetrical diphosphite L1, as well as its two monophosphite constituents L2 and L3, toward hydrolysis was investigated by means of in situ NMR spectroscopy under similar conditions as applied in industry. Hydrolysis pathways, intermediates, and kinetics were clarified. DFT calculations were used to support the experimentally found data. The acylphosphite unit L2, which reacts with water in an unselective manner, was proven to be much less stable than the phenolphosphite L3. The stability of the bidentate ligand L1 can be therefore mainly attributed to its phenolphosphite moiety. With an excess of water, the hydrolysis of L1 and L2 as well as their Rh-complexes is first-order with respect to the phosphite. Surprisingly, coordination to Rh significantly stabilizes the monodentate ligand L2, while in strong contrast, the bidentate ligand L1 decomposes faster in the Rh complex. NMR spectroscopy provided evidence for the existence of species from decomposition of phosphites, which can likewise coordinate as ligands to the metal. Electron-withdrawing groups in the periphery of the acylphosphite moiety decrease the stability of L1, whereas 3,5-disubstituted salicylic acid derivatives with bulky groups showed superior stability. These modifications of L1 also give rise to different catalytic performances in the n-regioselective hydroformylation of n-octenes and 2-pentene, from which the 3,5-di-t-butyl-substituted ligand offered a higher n-regioselectivity accompanied by a lowering of the reaction rate in comparison to the parent ligand L1.
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    Effects of substitution pattern in phosphite ligands used in rhodium-catalyzed hydroformylation on reactivity and hydrolysis stability
    (Basel : MDPI, 2019) Kloß, Svenja; Selent, Detlef; Spannenberg, Anke; Franke, Robert; Börner, Armin; Sharif, Muhammad
    The stability of homogeneous catalytic systems is an industrially crucial topic, which, however, receives comparatively little attention from academic research. Phosphites are among the most frequently used ligands in industrial, rhodium-catalyzed n-regioselective hydroformylation. However, they are particularly vulnerable to hydrolysis. Since the decomposition of ligands should be dependent on the substitution patterns, phenyl, tert-butyl and condensed ring systems of benzopinacolphosphites were evaluated concerning their activity, regioselectivity and hydrolysis stability. A series of twelve strongly related phosphites were synthesized, tested in the hydroformylation of isomeric n-octenes, and studied in hydrolysis experiments using in situ NMR spectroscopy. Our results show that substituents in the ortho-position, especially tert-butyl substituents, enhance hydrolysis stability while maintaining compelling activity and regioselectivity. In contrast, substituents in the para-position may destabilize the phosphite. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.