Mechanistic studies on the formation of Pt(II) hydroformylation catalysts in imidazolium-based ionic liquids

Illner, Peter; Zahl, Achim; Puchta, Ralph; Hommes, Nicolaas J. R. van Eikema; Wasserscheid, Peter; Eldik, Rudi van

doi:10.1016/j.jorganchem.2005.03.029

Cited by 94 publications

(57 citation statements)

References 21 publications

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“…Structure optimisations at this level, probed for selected systems, were found to yield essentially the same results. The approximation of solvent effects by the polarisable continuum model (PCM) [78] or the isodensity molecular surface polarisable continuum model (IPCM) [79] unfortunately failed for some systems, [80,81] but where successful, they agreed with the CPCM results. The Gaussian 03 suite of programs was used throughout.…”

Section: Methodsmentioning

confidence: 89%

Ligand‐Exchange Processes on Solvated Lithium Cations: DMSO and Water/DMSO Mixtures

et al. 2007

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Solutions of LiClO(4) in solvent mixtures consisting of dimethylsulfoxide (DMSO) and water, or DMSO and gamma-butyrolactone, were studied by (7)Li NMR spectroscopy (for complexation by cryptands in gamma-butyrolactone as a solvent, see: E. Pasgreta, R. Puchta, M. Galle, N. J. R. van Eikema Hommes, A. Zahl, R. van Eldik, J. Incl. Phen., 2007, 58, 81-88). Chemical shifts indicate that the Li(+) ion is coordinated by four DMSO molecules. In the binary solvent mixture of water and DMSO, no selective solvation is detected, thus indicating that on increasing the water content of the solvent mixture, DMSO is gradually displaced by water in the coordination sphere of Li(+). The ligand-exchange mechanism of Li(+) ions solvated by DMSO and water/DMSO mixtures was studied using DFT calculations. Ligand exchange on [Li(DMSO)(4)](+) was found to follow a limiting associative (A) mechanism. The displacement of coordinated H(2)O by DMSO in [Li(H(2)O)(4)](+) follows an associative interchange mechanism. The suggested mechanisms are discussed in reference to available experimental and theoretical data.

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Section: Methodsmentioning

confidence: 89%

Ligand‐Exchange Processes on Solvated Lithium Cations: DMSO and Water/DMSO Mixtures

et al. 2007

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“…Materials: The RTIL [bmim]A C H T U N G T R E N N U N G [NTf 2 ] was synthesised according to a known procedure [52] and was kept under a nitrogen atmosphere. The water content of this ionic liquid was determined by Karl-Fischer titration by using a Metrohm 765 KF Coulomb meter and was found to be 55 ppm.…”

Section: Methodsmentioning

confidence: 99%

Multiple Mechanisms for Electron Transfer at Metal/Self‐Assembled Monolayer/Room‐Temperature Ionic Liquid Junctions: Dynamical Arrest versus Frictional Control and Non‐Adiabaticity

Khoshtariya

Dolidze

Eldik

2009

Chemistry A European J

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Electrochemical devices consisting of gold electrodes coated by electronically well-behaved self-assembled alkanethiol monolayers of variable thickness, a ferrocene/ferrocenium redox probe and a typical room-temperature ionic liquid (RTIL) [bmim][NTf(2)] (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) as a unique reaction medium with an exceptionally broad spectrum of relaxational modes (probed under variable temperature and pressure conditions), have been used to vary the intrinsic electron-transfer (ET) rate constant over eight orders of magnitude (from 0.1 to 3x10(7) s(-1)) by further tuning of the overvoltage. A remarkable interplay of ET mechanisms was observed, which was accompanied by the stepwise drop in the reorganisation free energy of the medium from 1.0 to 0.1 eV. The first mechanistic changeover to the dynamically arrested regime, with a locking ultra-slow relaxation time of approximately 50 micros, occurred at donor-acceptor separations below 20 A. Another mechanistic changeover to the full solvent friction regime, controlled by a medium relaxation process of approximately 100 ns, emerged for ET distances smaller than 8 A.

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“…162 The energy of transition state representing the SnCl 2 is by 2.8 kcal mol À1 lower in energy, than the reactants cis-…”

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confidence: 94%

Computational aspects of hydroformylation

Kégl

2015

RSC Adv.

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The influence of transition metal complexes as catalysts upon the activity and selectivity of hydroformylation reactions has been extensively investigated during the last decades. Nowadays computational chemistry is an indispensable tool for elucidation of reaction mechanisms and for understanding the various aspects which govern the outcome of catalytic reactions. This review attempts to survey the recent literature concerning computational studies on hydroformylation and theoretical coordination chemistry results related to hydroformylation.

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Mechanistic studies on the formation of Pt(II) hydroformylation catalysts in imidazolium-based ionic liquids

Cited by 94 publications

References 21 publications

Ligand‐Exchange Processes on Solvated Lithium Cations: DMSO and Water/DMSO Mixtures

Ligand‐Exchange Processes on Solvated Lithium Cations: DMSO and Water/DMSO Mixtures

Multiple Mechanisms for Electron Transfer at Metal/Self‐Assembled Monolayer/Room‐Temperature Ionic Liquid Junctions: Dynamical Arrest versus Frictional Control and Non‐Adiabaticity

Computational aspects of hydroformylation

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