High-oxidation-state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin-state preferences of threefold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(Im)}FeN], R = Bu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(Im)}Fe(NR')], R = Mes, R' = 1-adamantyl (3), Bu (4), were investigated by electronic absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMEN)FeN] (TIMEN = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), were investigated by Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (for 3 and 4) and frequency-domain Fourier-transform (FD-FT) terahertz electron paramagnetic resonance (for 3), which reveal their zero-field splitting parameters. Experimentally correlated theoretical studies comprising ligand-field theory and quantum chemical theory, the latter including both density functional theory and ab initio methods, reveal the key role played by the Fe 3d (a) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin-state preference of the complex. The ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.
Mononuclear copper(II) salen‐type Schiff base complexes, CuIIL1–5 [H2L1 to H2L5 = tetradentate N,N,O,O ligands derived from 2‐hydroxybenzaldehyde, 2,4‐dihydroxybenzaldehyde, 3,5‐dibromo‐2‐hydroxybenzaldehyde, 2‐hydroxy‐5‐nitrobenzaldehyde, 5‐chloro‐2‐hydroxybenzaldehyde and 1,3‐bis(3‐aminopropyl)tetramethyldisiloxane, respectively] were prepared in situ in the presence of a copper(II) salt or by direct complexation between a copper(II) salt and a presynthesised Schiff base. The compounds {CuL1, CuL1·0.5Py, CuL2·0.375CH2Cl2, (CuL3)[Cu(4‐Me‐Py)4Cl]Cl·2H2O, CuL4, CuL4·CHCl3 and CuL5, as well as the isolated ligand H2L3} were characterised by elemental analysis, spectroscopic methods (IR, UV/Vis, 1H NMR, EPR) and X‐ray crystallography. The formation of a 12‐membered central chelate ring in these complexes is effected by the tetramethyldisiloxane unit, which separates the aliphatic chains, thus significantly reducing the mechanical strain in such a chelate ring. We dub this a “shoulder yoke effect” by analogy with the load‐spreading ability of such an ancient device. The coordination geometry of copper(II) in CuIIL1–5 can be described as tetrahedrally distorted square‐planar. Maximum tetrahedral distortion of the coordination geometry expressed by the parameter τ4 was observed for CuL1 (0.460), while distortion was minimal for the two crystallographically independent molecules of CuL2 (0.219 and 0.284). The Si–O–Si bond angle varies markedly between 169.75(2)° for CuL1 and 154.2(3)° for CuL4·CHCl3. Charge‐density and DFT calculations on CuL1 indicate high ionic character of the Si–O bonds in the tetramethyldisiloxane fragment. The new copper(II) complexes bearing the disiloxane moiety have been shown to act as catalyst precursors for the aerobic oxidation of benzyl alcohol to benzaldehyde mediated by the TEMPO radical, reaching yields and TONs up to 99 % and 990, respectively, under mild and environmentally friendly conditions (50 °C; MeCN/H2O, 1:1).
Six dinuclear vanadium(V) complexes have been synthesized: NH4[(VO2)2((H)LH)] (NH4[1]), NH4[(VO2)2((t-Bu)LH)] (NH4[2]), NH4[(VO2)2((Cl)LH)] (NH4[3]), [(VO2)(VO)((H)LH)(CH3O)] (4), [(VO2)(VO)((t-Bu)LH)(C2H5O)] (5), and [(VO2)(VO)((Cl)LH)(CH3O)(CH3OH/H2O)] (6) (where (H)LH4 = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone, (t-Bu)LH4 = 1,5-bis(3,5-di-tert-butyl-2-hydroxybenzaldehyde)carbohydrazone, and (Cl)LH4 = 1,5-bis(3,5-dichloro-2-hydroxybenzaldehyde)carbohydrazone). The structures of NH4[1] and 4-6 have been determined by X-ray diffraction (XRD) analysis. In all complexes, the triply deprotonated ligand accommodates two V ions, using two different binding sites ONN and ONO separated by a diazine unit -N-N-. In two pockets of NH4[1], two identical VO2(+) entities are present, whereas, in those of 4-6, two different VO2(+) and VO(3+) are bound. The highest oxidation state of V ions was corroborated by X-ray data, indicating the presence of alkoxido ligand bound to VO(3+) in 4-6, charge density measurements on 4, magnetic susceptibility, NMR spectroscopy, spectroelectrochemistry, and density functional theory (DFT) calculations. All four complexes characterized by XRD form dimeric associates in the solid state, which, however, do not remain intact in solution. Compounds NH4[1], NH4[2], and 4-6 were applied as alternative selective homogeneous catalysts for the industrially significant oxidation of cyclohexane to cyclohexanol and cyclohexanone. The peroxidative (with tert-butyl hydroperoxide, TBHP) oxidation of cyclohexane was performed under solvent-free and additive-free conditions and under low-power microwave (MW) irradiation. Cyclohexanol and cyclohexanone were the only products obtained (high selectivity), after 1.5 h of MW irradiation. Theoretical calculations suggest a key mechanistic role played by the carbohydrazone ligand, which can undergo reduction, instead of the metal itself, to form an active reduced form of the catalyst.
Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing a disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed by addition of the appropriate metal(II) salt. The ligand H2L resulting from these reactions is a 2:1 condensation product of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The resulting metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, and MnL(OAc)·0.15H2O, were characterized by elemental analysis, spectroscopic methods (IR, UV-vis, X-band EPR, HFEPR, (1)H NMR), ESI mass spectrometry, and single crystal X-ray diffraction. Taking into account the well-known strong stabilizing effects of tert-butyl groups in positions 3 and 5 of the aromatic ring on phenoxyl radicals, we studied the one-electron and two-electron oxidation of the compounds using both experimental (chiefly spectroelectrochemistry) and computational (DFT) techniques. The calculated spin-density distribution and localized orbitals analysis revealed the oxidation locus and the effect of the electrochemical electron transfer on the molecular structure of the complexes, while time-dependent DFT calculations helped to explain the absorption spectra of the electrochemically generated species. Hyperfine coupling constants, g-tensors, and zero-field splitting parameters have been calculated at the DFT level of theory. Finally, the CASSCF approach has been employed to theoretically explore the zero-field splitting of the S = 2 MnL(OAc) complex for comparison purposes with the DFT and experimental HFEPR results. It is found that the D parameter sign strongly depends on the metal coordination geometry.
The success of innovative drugs depends on an interdisciplinary and holistic approach to their design and development. The supramolecular architecture of living systems is controlled by non-covalent interactions to a very large extent. The latter are prone to extensive cooperation and like a virtuoso play a symphony of life. Thus, the design of effective ligands should be based on thorough knowledge on the interactions at either a molecular or high topological level. In this work, we emphasize the importance of supramolecular structure and ligand-based design keeping the potential of supramolecular H-bonding synthons in focus. In this respect, the relevance of supramolecular chemistry for advanced therapies is appreciated and undisputable. It has developed tools, such as Hirshfeld surface analysis, using a huge data on supramolecular interactions in over one million structures which are deposited in the Cambridge Structure Database (CSD). In particular, molecular interaction surfaces are useful for identification of macromolecular active sites followed by in silico docking experiments. Ornithine-derived compounds are a new, promising class of multi-targeting ligands for innovative therapeutics and cosmeceuticals. In this work, we present the synthesis together with the molecular and supramolecular structure of a novel ornithine derivative, namely N-α,N-δ)-dibenzoyl-(α)-hydroxymethylornithine, 1. It was investigated by modern experimental and in silico methods in detail. The incorporation of an aromatic system into the ornithine core induces stacking interactions, which are vital in biological processes. In particular, rare C=O…π intercontacts have been identified in 1. Supramolecular interactions were analyzed in all structures of ornithine derivatives deposited in the CSD. The influence of substituent was assessed by the Hirshfeld surface analysis. It revealed that the crystal packing is stabilized mainly by H…O, O…H, C…H, Cl (Br, F)…H and O…O interactions. Additionally, π…π, C-H…π and N-O…π interactions were also observed. All relevant H-bond energies were calculated using the Lippincott and Schroeder H-bond model. A library of synthons is provided. In addition, the large synthons (Long-Range Synthon Aufbau Module) were considered. The DFT optimization either in vacuo or in solutio yields very similar molecular species. The major difference with the relevant crystal structure was related to the conformation of terminal benzoyl C15-C20 ring. Furthermore, in silico prediction of the extensive physicochemical ADME profile (absorption, distribution, metabolism and excretion) related to the drug-likeness and medicinal chemistry friendliness revealed that a novel ornithine derivative 1 has the potential to be a new drug candidate. It has shown good in silico absorption and very low toxicity.
Camptothecin (CPT) is an anticancer drug that inhibits topoisomerase I (Topo I), an enzyme closely linked to cell division, by forming a ternary DNA−CPT−Topo I complex. However, it has been shown that UVA-irradiated CPT in the absence of Topo I produces DNA damage. It has been proposed that free radicals are the key species responsible for the DNA cleavage. It has also been shown that the presence of metal ions enhances the activity of several anticancer drugs. Therefore, we attempt here to explore and identify free radicals generated in these processes. We describe a detailed spectroscopic study of UVA-irradiated CPT and the Cu(II)−CPT complex. From the low-temperature EPR spectrum of the Cu(II)−CPT complex, a proximity between the Cu(II) ion and the 20-hydroxy group of the lactone E ring of CPT is proposed. Upon irradiation (λ = 365 nm) of the Cu(II)−CPT complex in deoxygenated dimethyl sulfoxide (DMSO), the EPR signal of Cu(II) measured in situ at room temperature shows formal first-order exponential decay with a formal half-life of 11 min. By the use of a specific Cu(I) chelating agent, neocuproine, it was shown that, during this process, Cu(II) is reduced to Cu(I). When the photochemical experiments are repeated in oxygen-saturated DMSO solutions, analogous phenomena are observed, characterized by a formal half-life of 16 min for Cu(II), except that there is an induction period of ∼3 min. Application of the spin-trap agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO) shows that during this induction period the only radical formed is the superoxide radical, trapped as the •DMPO−O2 - adduct. The loss in EPR signal intensity of the Cu(II)−CPT complex upon irradiation is accompanied by the appearance of a new EPR signal at g ≈ 2.0022. Application of the spin traps nitrosodurene (ND) and DMPO revealed that the main radical product formed upon continuous irradiation of CPT in DMSO solutions is the hydroxyl radical (trapped in DMSO as the •CH3 adduct). Application of 2,2,6,6-tetramethyl-4-piperidinol has revealed that irradiation of CPT in aerated DMSO solution also leads to the formation of singlet oxygen (1O2). In the Cu(II)−CPT system, the formation of methyl radicals is suppressed, and the generation of two new radical adducts originating from camptothecin ring cleavage is identified. A mechanism of photochemically generated radicals that include the superoxide radical and the radical cation of the {Cu(II)···CPT•+} complex followed by the reduction of Cu(II) to Cu(I) is proposed. The EPR experiments on irradiated CPT in the absence of copper (II) support the importance of the 20-hydroxy group of the lactone E ring in the antitumor activity of the drug mediated through the initially generated hydroxyl radical. In the presence of Cu(II), there is blockage of the 20-hydroxy group of CPT, and the generation of hydroxyl radicals is strongly suppressed. In this case, there is a mixture of radicals of various origin generated as a result of irradiation, which are capable of causing DNA damage. We propose that the superoxid...
The redox properties of copper, nickel, and cobalt complexes (MePh 3 P)[M(bdt) 2 ] with the ligand benzene-1,2-dithiolate (bdt) and synthesized complexes (MePh 3 P)[M(bdtCl 2 ) 2 ] with the ligand 3,6-dichlorobenzene-1,2-dithiolate (bdtCl 2 ) have been studied by cyclic voltammetry and in situ EPR−UV/vis/NIR spectroelectrochemistry. The addition of chlorine substituents to the 3-and 6-positions of the benzene ring not only facilitates the reduction of [M(bdtCl 2 ) 2 ] − complexes but also leads to the remarkable stabilization of [M(bdtCl 2 ) 2 ] 2− dianions in solution. In contrast to the EPR-silent copper complexes, the solutions of nickel samples exhibit a broad singlet EPR signal at room temperature which becomes anisotropic at 100 K with a characteristic rhombic pattern. Cathodic reduction of copper and cobalt complexes leads to paramagnetic species having an EPR signal with splitting from 63,65 Cu for copper and from 59 Co for cobalt samples, confirming a strong contribution of the central atom with substantial delocalization of the unpaired spin onto the central atom. B3LYP/6-311g*/pcm calculations of the monoanions as well as of their oxidized and reduced forms were performed. The spin density of all open-shell ground states calculated for the investigated complexes in different redox states corresponds well to the experimental spectroelectrochemical data.
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