Monomer−Dimer Equilibria of Oxo/Imido Complexes of Heptavalent Rhenium: Theoretical and Spectroscopic Investigations

Gisdakis, Philip; Rösch, Notker; Bencze, Éva; Mink, J.; Gonçalves, Isabel??S.; Kühn, Fritz??E.

doi:10.1002/1099-0682(200104)2001:4<981::aid-ejic981>3.3.co;2-6

Cited by 7 publications

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“…The dimerisation energy is –21.8 kJ · mol –1 (without corrections) and –15.9 kJ · mol –1 (after CP and ZPVE corrections), falling in the expected range for this type of interaction 7–14. These values show that a C–H ··· O bonded dimer is clearly more stable than the previously reported dimers based on oxygen bridges 6. In fact, the dimerisation energy for oxygen bridged dimers, evaluated at the same level of theory, ranges from 7.1 kJ · mol –1 to 148.4 kJ · mol –1 as mentioned above.…”

Section: Resultsmentioning

confidence: 69%

“…The structure of this compound has been previously reported 2–6. These studies include single crystal neutron diffraction structure determination,3 as well as several vibrational studies combined with ab initio calculations 2,4–6. However, some questions concerning the intermolecular interactions in the liquid and solid phases still remain.…”

Section: Introductionmentioning

confidence: 99%

“…However, some questions concerning the intermolecular interactions in the liquid and solid phases still remain. In a recent work by Gisdakis et al, it was proposed that MTO can associate into dimers through oxo‐bridges,6 where two Re atoms are bound by two Re–O–Re bridges in order to preserve the stoichiometry. Ab initio calculations predicted that the formation of the four proposed geometries would be endothermic, with dimerization energies of between 7.1 kJ·mol –1 and 148.4 kJ · mol –1 6…”

Section: Introductionmentioning

confidence: 99%

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The Role of C–H···O Interactions in the Solid and Liquid‐Phase Structures of Methyltrioxo Rhenium

Vaz

Ribeiro‐Claro

2005

Eur J Inorg Chem

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Keywords: Rhenium / C-H···O Hydrogen bonds / Ab initio calculations / Raman spectroscopy / Inelastic neutron scatteringThe importance of C-H···O hydrogen bonds involving the less common Re=O acceptor group in the small organometallic methyltrioxorhenium (MTO) is studied by combined vibrational spectroscopy and ab initio calculations. The observed vibrational spectrum is well described by the calculated spectrum of a C-H···O bonded dimer, which accounts for the symmetry decrease and the intermolecular interactions in the solid. Spectral evidence indicates both C-H···O and O-H···O hydrogen bonds are formed in the MTO/meth-

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Section: Resultsmentioning

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Role of C–H···O Interactions in the Solid and Liquid‐Phase Structures of Methyltrioxo Rhenium

Vaz

Ribeiro‐Claro

2005

Eur J Inorg Chem

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“…The tetramer already provides a good model for the interpretation of the IR and Raman spectra of poly-MTO and assigns the bridging oxygen atoms as the best candidates to bind the excess protons present in poly-MTO [37]. Terminal oxygens of monomeric MTO seem to be easily available for the formation of bridging oxygens [38]. …”

Section: Behavior Of Methyltrioxorhenium In Watermentioning

confidence: 99%

Methyltrioxorhenium and its applications in olefin oxidation, metathesis and aldehyde olefination

Kühn

Scherbaum

Herrmann

2004

Journal of Organometallic Chemistry

200

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“…Other related RReO 3 molecules are well known, but they differ in their behavior and properties, including catalytic and photochemical activity . Several theoretical studies have addressed different aspects of the chemistry of MTO, namely, the homolysis of the Re−C bond, but to our knowledge, none have addressed the photochemistry of MTO and other trioxorhenim complexes by means of modern quantum-chemical calculations.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of Methyltrioxorhenium Revisited: A DFT/TD-DFT and CASSCF/MS-CASPT2 Theoretical Study

et al. 2006

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The electronic structure of (CH3)ReO3 was reanalyzed by means of DFT calculations (ADF and Gaussian03 programs). TD-DFT calculations were carried out, using the DFT-optimized structure and several functionals, to assign the electronic excitations and interpret the dissociative behavior under irradiation. The agreement between calculated and experimental wavelengths was very good and could not be improved when using highly correlated methods (CASSCF/MS-CASPT2). The lowest energy transition at 260 nm was assigned to a LMCT from p O to Re d (π* Re−O), correcting the earlier empirical assignment. The second transition, experimentally observed at 240 nm, is assigned to a charge transfer from C and O to Re in TD-DFT, but the weight of the C participation drops significantly in the CASSCF/MS-CASPT2 approach. (C2H5)ReO3 exhibits a similar behavior. On the other hand, for (C6H5)ReO3 and {C6H3(CH3)3}ReO3 the strong low-energy absorption results from a LMCT from the phenyl π* to d Re (π* Re−O), reproducing the experimental trends.

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Monomer−Dimer Equilibria of Oxo/Imido Complexes of Heptavalent Rhenium: Theoretical and Spectroscopic Investigations

Cited by 7 publications

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The Role of C–H···O Interactions in the Solid and Liquid‐Phase Structures of Methyltrioxo Rhenium

The Role of C–H···O Interactions in the Solid and Liquid‐Phase Structures of Methyltrioxo Rhenium

Methyltrioxorhenium and its applications in olefin oxidation, metathesis and aldehyde olefination

Photochemistry of Methyltrioxorhenium Revisited: A DFT/TD-DFT and CASSCF/MS-CASPT2 Theoretical Study

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