Browsing by Subject "Aromaticity"

Now showing 1 - 4 of 4
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    Analysis of non-innocence of phosphaquinodimethane ligands when charge and aromaticity come into play
    (Wiley, 2021-06-25) Junker, Philip; Rey Planells, Alicia; Espinosa Ferao, Arturo; Streubel, Rainer; Química Orgánica
    Several phosphaquinodimethanes and their M(CO)5 complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH2 substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.
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    Carbonylation of Boranes ¿ A Computational Study
    (Royal Society of Chemistry, 2023-12-11) Espinosa Ferao, Arturo Francisco; Química Orgánica
    The classical simple picture of stepwise B-to-C migratory insertion of all three alkyl groups in the carbonylation reaction of trialkyl boranes with CO was shown not to be correct, except for the first alkyl group shift affording an acyl borane. The second and third direct alkyl shifts turned out to be kinetically hampered due to the non-activated character of the B C bond in electron-poor B atoms. The latter can only be achieved by either the autocatalytic action of the final alkyl boron oxide or by formation of dimeric species with weakened B-alkyl bonds at borate centres. Both thermodynamic and several NICS-related parameters pointed to scarce, even “negative”, aromatic character for boroxines, the final cyclotrimerization products of alkyl-boron oxides
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    Ring strain energies of three-membered homoatomic inorganic rings El3 and diheterotetreliranes El2Tt (Tt = C, Si, Ge): accurate versus additive approaches
    (American Chemical Society, 2022-09-05) Rey Planells, Alicia; Espinosa Ferao, Arturo; Química Orgánica
    Accurate ring strain energies (RSEs) for three-membered symmetric inorganic rings El3 and organic dihetero-monocycles El2C and their silicon El2Si and germanium El2Ge analogues have been computed for group 14–16 “El” heteroatoms using appropriate homodesmotic reactions and calculated at the DLPNO-CCSD-(T)/def2-TZVPP//B3LYP-D4/def2-TZVP(ecp) level. Rings containing triels and Sn/Pb heteroatoms are studied as exceptions to the RSE calculation as they either do not constitute genuine rings or cannot use the general homodesmotic reaction scheme due to uncompensated interactions. Some remarkable concepts already related to the RSE such as aromaticity or strain relaxation by increasing the s-character in the lone pair (LP) of the group 15–16 elements are analyzed extensively. An appealing alternative procedure for the rapid estimation of RSEs using additive rules, based on contributions of ring atoms or endocyclic bonds, is disclosed.
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    Ring strain energy of diheteropnictogeniranes El2Pn (Pn=N, P, As, Sb)– Accurate versus additive approaches
    (Wiley, 2023-11-08) Espinosa Ferao, Arturo; Rey Planells, Alicia; Química Orgánica
    Accurate ring strain energy (RSE) values for sixty-six parent pnictogeniranes having two other identical p-block elements, El2Pn, have been reported. A decrease in RSE was observed to correlate with an increase in the p character of the AO used in endocyclic bonds, which is particularly remarkable on descending the groups 15 and 16. The latter also parallels higher -NICS(1) values, which seems not to be related with an increase in aromaticity, as pointed out by other NICS-related criteria, but to atom-centred diatropic currents mostly arising from the presence of lone pairs. Only in case of pnictogenaditrieliranes Tr2Pn (Tr=B, Al, Ga), the decrease of -NICS(1) is related to a lower Hückel-type 2π-electron aromaticity on descending group 13. The use of an additive methodology based on atom-strain contributions enables estimation of RSEs for a large majority of all possible three-membered rings containing group 13–16 elements with modest accuracy (RMSE=4.371 kcal/mol), that could be remarkably improved by using bond-strain contributions (RMSE=1.183 kcal/mol) instead.