RESUMO
Nickel complexes with a two-electron reduced CO2 ligand (CO2 2-, "carbonite") are investigated with regard to the influence alkali metal (AM) ions have as Lewis acids on the activation of the CO2 entity. For this purpose complexes with NiII(CO2)AM (AM=Li, Na, K) moieties were accessed via deprotonation of nickel-formate compounds with (AM)N(iPr)2. It was found that not only the nature of the AM ions in vicinity to CO2 affect the activation, but also the number and the ligation of a given AM. To this end the effects of added (AM)N(R)2, THF, open and closed polyethers as well as cryptands were systematically studied. In 14 cases the products were characterized by X-ray diffraction and correlations with the situation in solution were made. The more the AM ions get detached from the carbonite ligand, the lower is the degree of aggregation. At the same time the extent of CO2 activation is decreased as indicated by the structural and spectroscopic analysis and reactivity studies. Accompanying DFT studies showed that the coordinating AM Lewis acidic fragment withdraws only a small amount of charge from the carbonite moiety, but it also affects the internal charge equilibration between the LtBuNi and carbonite moieties.
RESUMO
Aiming at intramolecular frustrated Lewis pairs (FLPs) based on soft Lewis acidic bismuth centers, a phosphine function was combined with a dichloridobismuthane unit on a phenylene backbone utilizing a scrambling approach. The reaction between two equivalents of BiCl3 and (o-(Ph2P)C6H4)3Bi yielded (o-(Ph2P)C6H4)BiCl2(THF), the structure of which indicated Bi P interactions and thus a pronounced Lewis acidity at the bismuth center that was confirmed by the Gutmann-Beckett method. However, the system turned out to be insufficient to be utilized for FLP reactivity. Hence, the chloride ligands were exchanged by iodide and C2F5 substituents, respectively. Despite a lower electronegativity the iodide compound exhibits a shorter Bi P contact, while the C2F5 substituents led to a further decrease of the Lewis acidity, despite their high group electronegativity. DFT calculations rationalized this by a quenching of the Lewis acidity inherent to the σ*(Bi-C) orbital by negative hyperconjugation from occupied p-orbitals at the F atoms. Furthermore, it turned out that the strength of the covalent Bi-X σ-bond is a more important factor than the charge at Bi in determining the energetic accessibility and thus Lewis acidity of the antibonding σ*(Bi-C) orbital.
RESUMO
Nickel carbonite complexes supported by alkaline earth metals have been accessed via salt-metathesis of the corresponding alkali metal precursors. The new complexes undergo Schlenk-like exchange reactions in solution which have been investigated by NMR spectroscopy. Also their reactivity towards epoxides and carbon monoxide was studied.
RESUMO
The N3O macrocycle of the 12-TMCO ligand stabilizes a high spin (S = 5/2) [FeIII(12-TMCO)(OOtBu)Cl]+ (3-Cl) species in the reaction of [FeII(12-TMCO)(OTf)2] (1-(OTf)2) with tert-butylhydroperoxide (tBuOOH) in the presence of tetraethylammonium chloride (NEt4Cl) in acetonitrile at -20 °C. In the absence of NEt4Cl the oxo-iron(iv) complex 2 [FeIV(12-TMCO)(O)(CH3CN)]2+ is formed, which can be further converted to 3-Cl by adding NEt4Cl and tBuOOH. The role of the cis-chloride ligand in the stabilization of the FeIII-OOtBu moiety can be extended to other anions including the thiolate ligand relevant to the enzyme superoxide reductase (SOR). The present study underlines the importance of subtle electronic changes and secondary interactions in the stability of the biologically relevant metal-dioxygen intermediates. It also provides some rationale for the dramatically different outcomes of the chemistry of iron(iii)peroxy intermediates formed in the catalytic cycles of SOR (Fe-O cleavage) and cytochrome P450 (O-O bond lysis) in similar N4S coordination environments.