Berry Pseudorotation Mechanism for the Interpretation of the <sup>19</sup>F NMR Spectrum in PF<sub>5</sub> by Ab Initio Molecular Dynamics Simulations

Raynaud, Christophe; Maron, Laurent; Daudey, J. P.; Jolibois, Franck

doi:10.1002/cphc.200500297

Cited by 14 publications

(10 citation statements)

References 62 publications

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“…14,36 In some cases, accuracy could be significantly improved by including dynamic effects by means of molecular dynamic simulations, for example, in order to extract a statistical ensemble of molecular structures that would be used for NMR calculation purposes. 16,18 Another puzzling result is the very poor accuracy observed within basis set I, i.e. when ECPs are used for carbon and oxygen atoms.…”

Section: Discussionmentioning

confidence: 99%

“…5 An agreement with 10-20% deviation from experiment is often considered as good. In principle, theoretical accuracy can be increased by taking into account influences on the magnetic shielding: solvent effect, motion of the nuclei, 16 molecular vibrations. Accurate computations of NMR parameters become feasible owing to the ability to describe the effect of the surroundings with various methodological strategies (QM/MM, continuum solvent methods, 17 molecular dynamics of the solvent network 18 ).…”

Section: Introductionmentioning

confidence: 99%

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DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides

Rosal

Maron²,

Poteau³

et al. 2008

Dalton Trans.

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Transition metal hydrides are of great interest in chemistry because of their reactivity and their potential use as catalysts for hydrogenation. Among other available techniques, structural properties in transition metal (TM) complexes are often probed by NMR spectroscopy. In this paper we will show that it is possible to establish a viable methodological strategy in the context of density functional theory, that allows the determination of 1H NMR chemical shifts of hydride ligands attached to transition metal atoms in mononuclear systems and clusters with good accuracy with respect to experiment. 13C chemical shifts have also been considered in some cases. We have studied mononuclear ruthenium complexes such as Ru(L)(H)(dppm)2 with L = H or Cl, cationic complex [Ru(H)(H2O)(dppm)2]+ and Ru(H)2(dppm)(PPh3)2, in which hydride ligands are characterized by a negative 1H NMR chemical shift. For these complexes all calculations are in relatively good agreement compared to experimental data with errors not exceeding 20% except for the hydrogen atom in Ru(H)2(dppm)(PPh3)2. For this last complex, the relative error increases to 30%, probably owing to the necessity to take into account dynamical effects of phenyl groups. Carbonyl ligands are often encountered in coordination chemistry. Specific issues arise when calculating 1H or 13C NMR chemical shifts in TM carbonyl complexes. Indeed, while errors of 10 to 20% with respect to experiment are often considered good in the framework of density functional theory, this difference in the case of mononuclear carbonyl complexes culminates to 80%: results obtained with all-electron calculations are overall in very satisfactory agreement with experiment, the error in this case does not exceed 11% contrary to effective core potentials (ECPs) calculations which yield errors always larger than 20%. We conclude that for carbonyl groups the use of ECPs is not recommended, although their use could save time for very large systems, for instance in cluster chemistry. The reliance of NMR chemical shielding on dynamical effects, such as intramolecular rearrangements or trigonal twists, is also examined for H2Fe(CO)4, K+[HFe(CO)](-), HMn(CO)5 and HRe(CO)5. The accuracy of the theory is also examined for complexes with two dihydrogen ligands (Tp*RuH(H2)2 and [FeH(H2)(DMPE)2]+) and a ruthenium cluster, [H3Ru4(C6H6)4(CO)]+. It is shown that for all complexes studied in this work, the effect of the ligands on the chemical shielding of hydrogen coordinated to metal is suitably calculated, thus yielding a very good correlation between experimental chemical shifts and theoretical chemical shielding.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides

Rosal

Maron²,

Poteau³

et al. 2008

Dalton Trans.

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“…A similar behaviour is expected for [Pb(CO) 5 ] 2+ : static studies have shown properties close to those of the tetracoordinated species. 3 External dynamic simulations on [Cu(H 2 O) 5 ] +38 and PF 5 39 have reported such inversions.…”

Section: The [Pb(co) 4 ] 2+ Complexmentioning

confidence: 95%

Revisiting the holo- and hemidirected structural transition within the [Pb(CO)n]2+ model series using first-principles Molecular Dynamics

2011

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In this article, we resort to first-principles molecular dynamic simulations to examine the thermal effects on the structure of [Pb(CO)(n)](2+) complexes. Values of n are chosen to sample structures where hemidirected (n = 2, 4 and 6) or holodirected (n = 7 and 8) structures are found when using static approaches. In all cases, highly flexible structures are observed. In particular, hemidirectional distortions are characterized using geometrical and topological analysis. The octacarbonyl complex exhibits the decoordination of one of its carbonyl ligands at 300 K.

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“…At sufficiently high temperature, proton spectra of fluxional compounds consist in the superposition of several bonding situations. A relevant, but computationally expensive, way to take into account the motion of protons consists in performing molecular dynamics (MD) simulations at the ab initio or DFT level of theory and to average the theoretical spectroscopic data [10][11][12] . We have developed in our group a Car-Parrinello MD (CPMD) code using atom-centered basis functions, which is a tool of choice for taking into account the role of temperature on the motion of nuclei 13,14 , and to calculate several properties with quantum chemistry methods more familiar to theoretical chemists.…”

Section: Introductionmentioning

confidence: 99%

“…The importance of the Berry pseudorotation process in the interpretation of the 19 F NMR spectrum of phosphorus pentafluoride (PF 5 ) has been shown in Ref. 11. Ab initio MD (AIMD) simulations have been performed to generate a large number of geometries considered for NMR parameter computations at the DFT level.…”

Section: Introductionmentioning

confidence: 99%

Multicentered effective group potentials: ligand-field effects in organometallic clusters and dynamical study of chemical reactivity

et al. 2009

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A new multicentered effective group potential (EGP) is obtained for η 6-benzene. Applications on [Ru 4 (H) 4 (C 6 H 6) 4 ] n+ clusters (n=0 or 2) are in excellent agreement with reference DFT studies in terms of geometries, energies and electronic structures. In particular, the small singlet-triplet energy difference (3.8 kcal/mol) in [Ru 4 (H) 4 (C 6 H 6) 4 ] 2+ is very well reproduced. This new EGP is nevertheless not free from the limitations associated to this first generation of molecular pseudopotentials. A cautious analysis of the nature and exact role of this EGP is made, which provides new directions for the elaboration of the next generation of EGPs. In addition, the η 5-cyclopentadienyl EGP has been used to perform a constrained dynamical simulation for the reaction of Cp 2 LaH with H 2. The energy conservation during the simulation as well as the activation barrier extracted from the simulation clearly demonstrate the good behavior of this EGP in the context of molecular dynamics. Anharmonic effects on this reaction are underlined, further demonstrating the high accuracy of the potential energy surface obtained with EGPs. From a more general point of view, such EGPs are expected to provide accurate albeit low-cost ligand-field effects in organometallic clusters or nanoparticles and to allow dynamical studies at the surface of such compounds. Effective Group Potentials; ab initio molecular dynamics; organometallic clusters and nanoparticles; chemical reactivity

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Berry Pseudorotation Mechanism for the Interpretation of the ¹⁹F NMR Spectrum in PF₅ by Ab Initio Molecular Dynamics Simulations

Cited by 14 publications

References 62 publications

DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides

DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides

Revisiting the holo- and hemidirected structural transition within the [Pb(CO)n]2+ model series using first-principles Molecular Dynamics

Multicentered effective group potentials: ligand-field effects in organometallic clusters and dynamical study of chemical reactivity

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Berry Pseudorotation Mechanism for the Interpretation of the 19F NMR Spectrum in PF5 by Ab Initio Molecular Dynamics Simulations

Cited by 14 publications

References 62 publications

DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides

DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides

Revisiting the holo- and hemidirected structural transition within the [Pb(CO)n]2+ model series using first-principles Molecular Dynamics

Multicentered effective group potentials: ligand-field effects in organometallic clusters and dynamical study of chemical reactivity

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Berry Pseudorotation Mechanism for the Interpretation of the ¹⁹F NMR Spectrum in PF₅ by Ab Initio Molecular Dynamics Simulations