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Issue 31, 2010
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Chiral oxorhenium(V) complexes as candidates for the experimental observation of molecular parity violation: a structural, synthetic and theoretical study

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Abstract

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[double bond, length as m-dash]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.

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

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Publication details

The article was received on 27 Nov 2009, accepted on 30 Mar 2010 and first published on 07 Jun 2010


Article type: Paper
DOI: 10.1039/B925050F
Citation: Phys. Chem. Chem. Phys., 2010,12, 8792-8803
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    Chiral oxorhenium(V) complexes as candidates for the experimental observation of molecular parity violation: a structural, synthetic and theoretical study

    F. De Montigny, R. Bast, A. Severo Pereira Gomes, G. Pilet, N. Vanthuyne, C. Roussel, L. Guy, P. Schwerdtfeger, T. Saue and J. Crassous, Phys. Chem. Chem. Phys., 2010, 12, 8792
    DOI: 10.1039/B925050F

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