Coordination of Al(C$_6$F$_5$)$_3$ vs. B(C$_6$F$_5$)$_3$ on group 6 end-on dinitrogen complexes: chemical and structural divergences - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemical Science Année : 2024

Coordination of Al(C$_6$F$_5$)$_3$ vs. B(C$_6$F$_5$)$_3$ on group 6 end-on dinitrogen complexes: chemical and structural divergences

Résumé

The coordination of the Lewis superacid tris(pentafluorophenyl)alane (AlCF) to phosphine-supported, group 6 bis(dinitrogen) complexes [ML2(N2)2] is explored, with M = Cr, Mo or W and L = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), dmpe (1,2-bis(dimethylphosphino)ethane) or 2 × PMe2Ph. Akin to tris(pentafluorophenyl)borane (BCF), AlCF can form 1 : 1 adducts by coordination to one distal nitrogen of general formula trans-[ML2(N2){(μ-η1:η1-N2)Al(C6F5)3}]. The boron and aluminium adducts are structurally similar, showing a comparable level of N2 push–pull activation. A notable exception is a bent (BCF adducts) vs. linear (AlCF adducts) M–N–N–LA motif (LA = Lewis acid), explained computationally as the result of steric repulsion. A striking difference arose when the formation of two-fold adducts was conducted. While in the case of BCF the 2 : 1 Lewis pairs could be observed in equilibrium with the 1 : 1 adduct and free borane but resisted isolation, AlCF forms robust 2 : 1 adducts trans-[ML2{(μ-η1:η1-N2)Al(C6F5)3}2] that isomerise into a more stable cis configuration. These compounds could be isolated and structurally characterized, and represent the first examples of trinuclear heterometallic complexes formed by Lewis acid–base interaction exhibiting p and d elements. Calculations also demonstrate that from the bare complex to the two-fold aluminium adduct, substantial decrease of the HOMO–LUMO gap is observed, and, unlike the trans adducts (1 : 1 and 1 : 2) for which the HOMO was computed to be a pure d orbital, the one of the cis-trinuclear compounds mixes a d orbital with a π* one of each N2 ligands. This may translate into a more favourable electrophilic attack on the N2 ligands instead of the metal centre, while a stabilized N2-centered LUMO should ease electron transfer, suggesting Lewis acids could be co-activators for electro-catalysed N2 reduction. Experimental UV-vis spectra for the tungsten family of compounds were compared with TD-DFT calculations (CAM-B3LYP/def2-TZVP), allowing to assign the low extinction bands found in the visible spectrum to unusual low-lying MLCT involving N2-centered orbitals. As significant red-shifts are observed upon LA coordination, this could have important implications for the development of visible light-driven nitrogen fixation.
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hal-04633385 , version 1 (03-07-2024)

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Léon Escomel, Frederico F Martins, Laure Vendier, Anaïs Coffinet, Nicolas Queyriaux, et al.. Coordination of Al(C$_6$F$_5$)$_3$ vs. B(C$_6$F$_5$)$_3$ on group 6 end-on dinitrogen complexes: chemical and structural divergences. Chemical Science, 2024, 15 (24), pp.11321-11336. ⟨10.1039/d4sc02713b⟩. ⟨hal-04633385⟩
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