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Magnesium-halobenzene bonding: mapping the halogen sigma-hole with a Lewis-acidic complex.

ABSTRACT: Complexes of the Lewis base-free cations (^MeBDI)Mg⁺ and ( ^tBuBDI)Mg⁺ with Ph-X ligands (X = F, Cl, Br, I) have been studied (^MeBDI = HC[C(Me)N-DIPP]₂ and ^tBuBDI = HC[C(tBu)N-DIPP]₂; DIPP = 2,6-diisopropylphenyl). For the smaller β-diketiminate ligand (^MeBDI) only complexes with PhF could be isolated. Heavier Ph-X ligands could not compete with bonding of Mg to the weakly coordinating anion B(C₆F₅)₄ ^-. For the cations with the bulkier ^tBuBDI ligand, the full series of halobenzene complexes was structurally characterized. Crystal structures show that the Mg⋯X-Ph angle strongly decreases with the size of X: F 139.1°, Cl 101.4°, Br 97.7°, I 95.1°. This trend, which is supported by DFT calculations, can be explained with the σ-hole which increases from F to I. Charge calculation and Atoms-In-Molecules analyses show that Mg⋯F-Ph bonding originates from electrostatic attraction between Mg²⁺ and the very polar C ^δ+-F ^δ- bond. For the heavier halobenzenes, polarization of the halogen atom becomes increasingly important (Cl < Br < I). Complexation with Mg leads in all cases to significant Ph-X bond activation and elongation. This unusual coordination of halogenated species to early main group metals is therefore relevant to C-X bond breaking.

SUBMITTER: Friedrich A

PROVIDER: S-EPMC8179342 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:In the present work, a number of R-X⋯NH3 (X = Cl, Br, and I) halogen bonded systems were theoretical studied by means of DFT calculations performed at the ωB97XD/6-31+G(d,p) level of theory in order to get insights on the effect of the electron-donating or electron-withdrawing character of the different R substituent groups (R = halogen, methyl, partially fluorinated methyl, perfluoro-methyl, ethyl, vinyl, and acetyl) on the stability of the halogen bond. The results indicate that the relative stability of the halogen bond follows the Cl < Br < I trend considering the same R substituent whereas the more electron-withdrawing character of the R substituent the more stable the halogen bond. Refinement of the latter results, performed at the MP2/6-31+G(d,p) level showed that the DFT and the MP2 binding energies correlate remarkably well, suggesting that the Grimme's type dispersion-corrected functional produces reasonable structural and energetic features of halogen bond systems. DFT results were also observed to agree with more refined calculations performed at the CCSD(T) level. In a further stage, a more thorough analysis of the R-Br⋯NH3 complexes was performed by means of a novel electron localization/delocalization tool, defined in terms of an Information Theory, IT, based quantity obtained from the conditional pair density. For the latter, our in-house developed C++/CUDA program, called KLD (acronym of Kullback-Leibler divergence), was employed. KLD results mapped onto the one-electron density plotted at a 0.04 a.u. isovalue, showed that (i) as expected, the localized electron depletion of the Br sigma-hole is largely affected by the electron-withdrawing character of the R substituent group and (ii) the R-X bond is significantly polarized due to the presence of the NH3 molecule in the complexes. The afore-mentioned constitutes a clear indication of the dominant character of electrostatics on the stabilization of halogen bonds in agreement with a number of studies reported in the main literature. Finally, the cooperative effects on the [Br-CN]n system (n = 1-8) was evaluated at the MP2/6-31+G(d,p) level, where it was observed that an increase of about ~14.2% on the complex stability is obtained when going from n = 2 to n = 8. The latter results were corroborated by the analysis of the changes on the Fermi-hole localization pattern on the halogen bond zones, which suggests an also important contribution of the electron correlation in the stabilization of these systems.

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Magnesium-halobenzene bonding: mapping the halogen sigma-hole with a Lewis-acidic complex.

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