RESUMEN

Bridging quinonoid ligands are important platforms for generating metal-based switchable optoelectronic and magnetic materials. A possible sound way of influencing the properties of the aforementioned materials is to modify the direct metal-ligand interface. We present herein a series of dinuclear RuII complexes where the set of donor atoms at the bridging quinonoid ligands range from [O,O,O,O], [O,O,O,N], [O,N,O,N] and [O,N,O,N']. Additionally, the substituents on the N-donors were varied as well (a total of eight different quinonoid bridges are compared). We also present a mononuclear RuII complex for comparison purposes. The dinuclear complexes act as switchable NIR dyes, absorbing in the NIR region in their mixed-valent RuII/RuIII form but not in the neighboring RuII/RuII and RuIII/RuIII states. The switching potentials (the potentials at which NIR absorptions appear) and the λmax of the NIR band can be fine-tuned by varying the donor atoms as well as the electron-donating ability of the substituents on the nitrogen atoms (tuning E by ca. 0.4 V and λmax by ca. 450 nm). Introducing more electron-rich substituents at the nitrogen atoms of the bridge results in higher band energies and more cathodic redox potentials. Unsymmetrical bridging ligands increase the thermodynamic stability of the mixed-valent state. Whereas almost all of the mixed-valent species presented here belong to the delocalised type III of the Robin-Day classification, the most unsymmetrical complex 2O,N(Mes) shows characteristic signs of a borderline Class-II-III compounds. This comprehensive study thus establishes the lesser used unsymmetrically substituted quinones as excellent bridges for generating and tuning a series of properties in their corresponding metal complexes.

RESUMEN

Activating chemical bonds through external triggers and understanding the underlying mechanism are at the heart of developing molecules with catalytic and switchable functions. Thermal, photochemical, and electrochemical bond activation pathways are useful for many chemical reactions. In this Article, a series of Ru(II) complexes containing a bidentate and a tripodal ligand were synthesized. Starting from all-pyridine complex 1(2+), the pyridines were stepwise substituted with "click" triazoles (2(2+)-7(2+)). Whereas the thermo- and photoreactivity of 1(2+) are due to steric repulsion within the equatorial plane of the complex, 3(2+)-6(2+) are reactive because of triazoles in axial positions, and 4(2+) shows unprecedented photoreactivity. Complexes that feature neither steric interactions nor axial triazoles (2(2+) and 7(2+)) do not show any reactivity. Furthermore, a redox-triggered conversion mechanism was discovered in 1(2+), 3(2+), and 4(2+). We show here ligand design principles required to convert a completely inert molecule to a reactive one and vice versa, and provide mechanistic insights into their functioning. The results presented here will likely have consequences for developing a future generation of catalysts, sensors, and molecular switches.

RESUMEN

Tuning of ligand properties is at the heart of influencing chemical reactivity and generating tailor-made catalysts. Herein, three series of complexes [Ru(L)(Cl)(X)]PF6 (X=DMSO, PPh3 , or CD3 CN) with tripodal ligands (L1-L5) containing pyridine and triazole arms are presented. Triazole-for-pyridine substitution and the substituent at the triazole systematically influence the redox behavior and photoreactivity of the complexes. The mechanism of the light-driven ligand exchange of the DMSO complexes in CD3 CN could be elucidated, and two seven-coordinate intermediates were identified. Finally, tuning of the ligand framework was applied to the catalytic oxygenation of alkanes, for which the DMSO complexes were the best catalysts and the yield improved with increasing number of triazole arms. These results thus show how click-derived ligands can be tuned on demand for catalytic processes.

RESUMEN

Reversible proton- and electron-transfer steps are crucial for various chemical transformations. The electron-reservoir behavior of redox non-innocent ligands and the proton-reservoir behavior of chemically non-innocent ligands can be cooperatively utilized for substrate bond activation. Although site-decoupled proton- and electron-transfer steps are often found in enzymatic systems, generating model metal complexes with these properties remains challenging. To tackle this issue, we present herein complexes [(cod-H)M(µ-L(2-)) M(cod-H)] (M = Pt(II), [1] or Pd(II), [2], cod = 1,5-cyclooctadiene, H2L = 2,5-di-[2,6-(diisopropyl)anilino]-1,4-benzoquinone), in which cod acts as a proton reservoir, and L(2-) as an electron reservoir. Protonation of [2] leads to an unusual tetranuclear complex. However, [1] can be stepwise reversibly protonated with up to two protons on the cod-H ligands, and the protonated forms can be stepwise reversibly reduced with up to two electrons on the L(2-) ligand. The doubly protonated form of [1] is also shown to react with OMe(-) leading to an activation of the cod ligands. The site-decoupled proton and electron reservoir sources work in tandem in a three-way cooperative process that results in the transfer of two electrons and two protons to a substrate leading to its double reduction and protonation. These results will possibly provide new insights into developing catalysts for multiple proton- and electron-transfer reactions by using metal complexes of non-innocent ligands.

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RESUMEN

Electrochemical and photochemical bond-activation steps are important for a variety of chemical transformations. We present here four new complexes, [Ru(L(n) )(dmso)(Cl)]PF6 (1-4), where L(n) is a tripodal amine ligand with 4-n pyridylmethyl arms and n-1 triazolylmethyl arms. Structural comparisons show that the triazoles bind closer to the Ru center than the pyridines. For L(2) , two isomers (with respect to the position of the triazole arm, equatorial or axial), trans-2sym and trans-2un , could be separated and compared. The increase in the number of the triazole arms in the ligand has almost no effect on the Ru(II) /Ru(III) oxidation potentials, but it increases the stability of the RuSdmso bond. Hence, the oxidation waves become more reversible from trans-1 to trans-4, and whereas the dmso ligand readily dissociates from trans-1 upon heating or irradiation with UV light, the RuS bond of trans-4 remains perfectly stable under the same conditions. The strength of the RuS bond is not only influenced by the number of triazole arms but also by their position, as evidenced by the difference in redox behavior and reactivity of the two isomers, trans-2sym and trans-2un . A mechanistic picture for the electrochemical, thermal, and photochemical bond activation is discussed with data from NMR spectroscopy, cyclic voltammetry, and spectroelectrochemistry.

RESUMEN

The compounds [Ru(bpy)2(L(1))](ClO4)2 (1(ClO4)2), [Ru(bpy)2(L(2))](ClO4)2 (2(ClO4)2), [Ru(bpy)2(L(3))](ClO4)2 (3(ClO4)2), [Ru(bpy)2(L(4))](ClO4)2 (4(ClO4)2), [Ru(bpy)2(L(5))](ClO4)2 (5(ClO4)2), and [Ru(bpy)2(L(6))](ClO4)2 6(ClO4)2 (bpy = 2,2'-bipyridine, L(1) = 1-(4-isopropyl-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L(2) = 1-(4-butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L(3) = 1-(2-trifluoromethyl-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L(4) = 4,4'-bis-{1-(2,6-diisopropyl-phenyl)}-1,2,3-triazole, L(5) = 4,4'-bis-{(1-phenyl)}-1,2,3-triazole, L(6) = 4,4'-bis-{1-(2-trifluoromethyl-phenyl)}-1,2,3-triazole) were synthesized from [Ru(bpy)2(EtOH)2](ClO4)2 and the corresponding "click"-derived pyridyl-triazole or bis-triazole ligands, and characterized by (1)H-NMR spectroscopy, elemental analysis, mass spectrometry and X-ray crystallography. Structural analysis showed a distorted octahedral coordination environment about the Ru(II) centers, and shorter Ru-N(triazole) bond distances compared to Ru-N(pyridine) distances in complexes of mixed-donor ligands. All the complexes were subjected to cyclic voltammetric studies, and the results were compared to the well-known [Ru(bpy)3](2+) compound. The oxidation and reduction potentials were found to be largely uninfluenced by ligand changes, with all the investigated complexes showing their oxidation and reduction steps at rather similar potentials. A combined UV-vis-NIR and EPR spectroelectrochemical investigation, together with DFT calculations, was used to determine the site of electron transfer in these complexes. These results provided insights into their electronic structures in the various investigated redox states, showed subtle differences in the spectroscopic signatures of these complexes despite their similar electrochemical properties, and provided clues to the unperturbed redox potentials in these complexes with respect to ligand substitutions. The reduced forms of the complexes display structured absorption bands in the NIR region. Additionally, we also present new synthetic routes for the ligands presented here using Cu-abnormal carbene catalysts.

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Bu4N[Fe(CO)3(NO)] displays unique catalytic properties in electron-transfer catalysis such as in allylic substitutions, hydrosilylation, transesterifications, or carbene transfer chemistry. Herein we present a detailed spectroelectrochemical investigation of this complex that unravels an interesting electrochemical-chemical transformation in which two parts of [Fe(CO)3(NO)](-) are oxidized and undergo a disproportionation in the presence of CO to [Fe(CO)5] and [Fe(CO)2(NO)2]. Upon re-reduction the former two complexes regenerate [Fe(CO)3(NO)](-) to about 85%.

RESUMEN

The article deals with the ruthenium complexes, [(bpy)Ru(Q')(2)] (1-3) incorporating two unsymmetrical redox-noninnocent iminoquinone moieties [bpy = 2,2'-bipyridine; Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, aryl = C(6)H(5) (Q'(1)), 1; m-Cl(2)C(6)H(3) (Q'(2)), 2; m-(OCH(3))(2)C(6)H(3) (Q'(3)), 3]. 1 and 3 have been preferentially stabilised in the cc-isomeric form while both the ct- and cc-isomeric forms of 2 are isolated [ct: cis and trans and cc: cis and cis with respect to the mutual orientations of O and N donors of two Q']. The isomeric identities of 1-3 have been authenticated by their single-crystal X-ray structures. The collective consideration of crystallographic and DFT data along with other analytical events reveals that 1-3 exhibit the valence configuration of [(bpy)Ru(II)(Q'(Sq))(2)]. The magnetization studies reveal a ferromagnetic response at 300 K and virtual diamagnetic behaviour at 2 K. DFT calculations on representative 2a and 2b predict that the excited triplet (S = 1) state is lying close to the singlet (S = 0) ground state with singlet-triplet separation of 0.038 eV and 0.075 eV, respectively. In corroboration with the paramagnetic features the complexes exhibit free radical EPR signals with g∼2 and (1)HNMR spectra with broad aromatic proton signals associated with the Q' at 300 K. Experimental results in conjunction with the DFT (for representative 2a and 2b) reveal iminoquinone based preferential electron-transfer processes leaving the ruthenium(ii) ion mostly as a redox insensitive entity: [(bpy)Ru(II)(Q'(Q))(2)](2+) (1(2+)-3(2+)) ⇋ [(bpy)Ru(II)(Q(')(Sq))(Q(')(Q))](+) (1(+)-3(+)) ⇋ [(bpy)Ru(II)(Q(')(Sq))(2)] (1-3) ⇋ [(bpy)Ru(II)(Q(')(Sq))(Q(')(Cat))](-)/[(bpy)Ru(III)(Q(')(Cat))(2)](-) (1(-)-3(-)). The diamagnetic doubly oxidised state, [(bpy)Ru(II)(Q'(Q))(2)](2+) in 1(2+)-3(2+) has been authenticated further by the crystal structure determination of the representative [(bpy)Ru(II)(Q'(3))(2)](ClO(4))(2) [3](ClO(4))(2) as well as by its sharp (1)H NMR spectrum. The key electronic transitions in each redox state of 1(n)-3(n) have been assigned by TD-DFT calculations on representative 2a and 2b.

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RESUMEN

Reactions of [{Ru(tmpa)}2(µ-Cl)2][ClO4]2, (2[ClO4]2, tmpa=tris(2-pyridylmethyl)amine) with 2,5-dihydroxy-1,4-benzoquinone (L1), 2,5-di-[2,6-(dimethyl)-anilino]-1,4-benzoquinone (L2), or 2,5-di-[2,4,6-(trimethyl)-anilino)]-1,4-benzoquinone (L3) in the presence of a base led to the formation of the dinuclear complexes [{Ru(tmpa)}2(µ-L1-2H)][ClO4]2 (3[ClO4]2), [{Ru(tmpa)}2(µ-L2-2H)][ClO4]2 (4[ClO4]2), and [{Ru(tmpa)}2(µ-L3-2H)][ClO4]2 (5[ClO4]2). Structural characterization of 5[ClO4]2 showed the localization of the double bonds within the quinonoid ring and a twisting of the mesityl substituents with respect to the quinonoid plane. Cyclic voltammetry of the complexes show two reversible oxidation and quinonoid-based reduction processes. Results obtained from UV/Vis/NIR and EPR spectroelectrochemistry are invoked to discuss ruthenium- versus quinonoid-ligand-centered redox activity. The complex 3[ClO4]2 is compared to the reported complex [{Ru(bpy)}2(µ-L1-2 H)]2+ (12+, bpy=2,2'-bipyridine). The effects of substituting the bidentate and better π-accepting bpy co-ligands with tetradentate tmpa ligands [pure σ-donating (amine) as well as σ-donating and π-accepting (pyridines)] on the redox and electronic properties of the complexes are discussed. Comparisons are also made between complexes containing the dianionic forms of the all-oxygen-donating L1 ligand with the L2 and L3 ligands containing an [O,N,O,N] donor set. The one-electron oxidized forms of the complexes show absorption in the NIR region. The position as well as the intensity of this band can be tuned by the substituents on the quinonoid bridge. In addition, this band can be switched on and off by using tunable redox potentials, making such systems attractive candidates for NIR electrochromism.

RESUMEN

We demonstrate the use of a Cu(I) catalyzed "Click" reaction in the synthesis of novel ligands for spin crossover complexes. The reaction between azides and alkynes was used to synthesize the reported tripodal ligand tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine, TBTA, and the new ligands tris[(1-cyclohexyl-1H-1,2,3-triazol-4-yl)methyl]amine, TCTA, and tris[(1-n-butyl-1H-1,2,3-triazol-4-yl)methyl]amine, TBuTA. Reactions of TBTA with Co(ClO(4))(2) lead to complexes of the form [Co(TBTA)(CH(3)CN)(3)](ClO(4))(2), 1, and [Co(TBTA)(2)](ClO(4))(2), 2, where complex formation can be controlled by the metal/ligand ratio and the complexes 1 and 2 can be chemically and reversibly switched from one form to another in solution resulting in coordination ambivalence. The benzyl substituents of TBTA in 2 show intramolecular C-H-π T-stacking that generates a chemical pressure to stabilize the low spin (LS) state at lower temperatures. The structural parameters of 2 are consistent with a Jahn-Teller active LS Co(II) (elongation) ion showing four short and two long bonds. 2 shows spin-crossover (SCO) behavior in the solid state and in solution with a high T(0) close to room temperature which is driven by the T-stacking. 1 remains high spin (HS) between 2 and 400 K. Reversible chemical switching is observed between 1 and 2 at room temperature, with an accompanying change in the spin state from HS to LS. The importance of the intramolecular T-stacking in driving the SCO behavior is proven by comparison with two analogous compounds that lack an aromatic substituent and remain HS down to very low temperatures.

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RESUMEN

The compounds 2-[2-(trifluoromethyl)-anilino]-5-hydroxy-1,4-benzoquinone (L(1)), 2,5-di-[2-(trifluoromethyl)-anilino]-1,4-benzoquinone (L(2)), 2-[2-(methylthio)-anilino]-5-hydroxy-1,4-benzoquinone (L(3)), and 2,5-di-[2-(methylthio)-anilino]-1,4-benzoquinone (L(4)) were prepared in high yields by reacting 2,5-dihydroxy-1,4-benzoquinone with the corresponding amines in a one-pot synthesis in refluxing acetic acid. This straightforward and "green" synthesis delivers biologically relevant asymmetric p-quinones such as L(1) and L(3) in a rare, simple, one-step process. The proposed synthetic route is general and can be applied to generate a variety of such molecules with different substituents on the nitrogen atoms. Structural characterization of L(2) and L(4) shows electron delocalization across the "upper" and "lower" parts of the molecule, thus showing the importance of charge separated species in the proper description of such molecules. Reactions of these ligands with [Cl(η(6)-Cym)Ru(µ-Cl)(2)Ru(η(6)-Cym)Cl] (Cym = p-Cymene = 1-isopropyl-4-methyl-benzene) in the presence of a base result in the formation of complexes [{Cl(η(6)-Cym)Ru}(2)(µ-L(-2H)(1))] (1), [{Cl(η(6)-Cym)Ru}(2)(µ-L(-2H)(2))] (2), [{Cl(η(6)-Cym)Ru}(2)(µ-L(-2H)(3))] (3), and [{Cl(η(6)-Cym)Ru}(2)(µ-L(-2H)(4))] (4). Structural characterization of 2 and 4 shows a rare syn-coordination of the chloride atoms. The SMe groups in 3 and 4 are not coordinated to the ruthenium center, and the bridging ligands thus function in a bis-bidentate form. Abstraction of the chloride atoms in these complexes with AgClO(4) in CH(3)CN results in the expected formation of solvent substituted complexes [{(CH(3)CN)(η(6)-Cym)Ru}(2)(µ-L(-2H)(1))][ClO(4)](2) (5[ClO(4)](2)) and [{(CH(3)CN)(η(6)-Cym)Ru}(2)(µ-L(-2H)(2))][ClO(4)](2) (6[ClO(4)](2)) with the ligands where there are no additional donor atoms on the nitrogen substituents. The same chloride abstraction reaction in the cases of 3 and 4 leads to an unprecedented substituent induced release of the Cym ligand, resulting in complexes of the form [(CH(3)CN)(η(6)-Cym)Ru(µ-L(-2H)(3))Ru(CH(3)CN)(3)][ClO(4)](2) (7[ClO(4)](2)) and [{(CH(3)CN)(3)Ru}(2)(µ-L(-2H)(4))][ClO(4)](2) (8[ClO(4)](2)), where the SMe groups are now coordinated to the metal center. In the case of complex 3, which contains an asymmetric bridging ligand, Cym release is observed only at the side that contains an additional SMe donor, thus proving the necessity of such donor substituents for the observed reactivity. The increase in Lewis acidity at the ruthenium center on chloride abstraction is made responsible for SMe coordination and the rigidity of the ligand systems, and their concomitant failure to coordinate in a "fac" manner as is required for a piano stool configuration results in the eventual Cym release. The bridging ligand which then coordinates in a bis-meridional fashion in 8[ClO(4)](2) results in a bis-pincer type of coordination. These observations were validated by a structural analysis of 8[ClO(4)](2). The results show the potential hemilabile character of ligands such as L(3) and L(4). Electrochemical and spectroscopic investigations are reported on 8[ClO(4)](2), and substitution reactions of the CH(3)CN molecules are presented to show the use of 8[ClO(4)](2) as a versatile precursor for other reactions.

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RESUMEN

The zinc-catalyzed addition of various alkynes to acylsilanes followed by a Zn-Brook rearrangement and either the Zn-ene-allene or Zn-yne-allene cyclization led to the enantio- and diastereoselective formation of carbocycles in a single-pot operation.