Titre :

Chiral oxorhenium(V) complexes as candidates for the experimental observation of molecular parity violation: a structural, synthetic and theoretical study.

Auteur(s) :

de Montigny, Frederic [Auteur]
Laboratoire Charles Friedel
Bast, Radovan [Auteur]
Centre for Theoretical and Computational Chemistry [CTCC]
Severo Pereira Gomes, Andre [Auteur]
Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 [PhLAM]
Pilet, Guillaume [Auteur]
Laboratoire des Multimatériaux et Interfaces [LMI]
Vanthuyne, Nicolas [Auteur]
ChiroSciences
Roussel, Christian [Auteur]
ChiroSciences
Guy, Laure [Auteur]
Laboratoire de Chimie - UMR5182 [LC]
Schwerdtfeger, Peter [Auteur]
Saue, Trond [Auteur]
Laboratoire de chimie quantique et de modélisation moléculaire [LCQMM]
Crassous, Jeanne [Auteur correspondant]
Institut des Sciences Chimiques de Rennes [ISCR]

Titre de la revue :

Physical Chemistry Chemical Physics

Pagination :

8792-803

Éditeur :

Royal Society of Chemistry

Date de publication :

2010-08-21

ISSN :

1463-9076

Mot(s)-clé(s) en anglais :

MIXED-LIGAND OXORHENIUM
NONCONSERVING ENERGY DIFFERENCE
ZINC-THIOLATE COMPLEXES
GAUSSIAN-BASIS SETS
WEAK-INTERACTIONS
BIOMOLECULAR HOMOCHIRALITY
ELECTROWEAK INTERACTIONS
VIBRATIONAL-SPECTRUM
BIOLOGICAL-ACTIVITY
CIRCULAR-DICHROISM

Discipline(s) HAL :

Chimie/Chimie théorique et/ou physique

Résumé en anglais : [en]

We report the synthesis and resolution of a series of new chiral "3 + 1" oxorhenium(V) complexes, designed for high-resolution laser spectroscopy experiments probing molecular parity-violation (PV) effects in the Re=O ...
Lire la suite >We report the synthesis and resolution of a series of new chiral "3 + 1" oxorhenium(V) complexes, designed for high-resolution laser spectroscopy experiments probing molecular parity-violation (PV) effects in the Re=O stretching mode frequency. These complexes display a particularly simple chemical structure, with the rhenium atom as the stereogenic center, and show large PV energy differences according to our calculations. They were obtained in the racemic and enantioenriched forms, in the latter case by using either semi-preparative chiral HPLC resolution or enantioselective synthesis. The vibrational transition frequency differences between the enantiomeric pairs due to PV have been calculated with two- and four-component relativistic Hamiltonians using Hartree-Fock (HF) and density functional theory (DFT). For three complexes, including one synthesized in enantioenriched form, our HF calculations predict frequency differences above the present resolution limit of 1 Hz. These results confirm the order of magnitude for the calculated HF PV vibrational frequency differences reported earlier for this class of compounds [P. Schwerdtfeger and R. Bast, J. Am. Chem. Soc., 2004, 126, 1652]. However, at the DFT level the PV vibrational frequency differences are in some cases reduced by an order of magnitude, but are still within the sensitivity of 0.01 Hz, which is the anticipated sensitivity in a new proposed experiment. We therefore believe that the present study represents an important step towards the experimental observation of PV in molecular systems, and emphasizes the extreme sensitivity of the PV vibrational frequency difference to the chemical environment around the rhenium center.Lire moins >

Langue :

Anglais

Vulgarisation :

Non

Collections :

• Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL