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1.
J Biomol Struct Dyn ; : 1-14, 2019 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-31411114

RESUMO

Five Schiff bases, 2-((3-chlorophenylimino)methyl)-5-(diethylamino)phenol (L1), 2-((2,4-dichlorophenylimino)methyl)-5-(diethylamino)phenol (L2), 5-(diethylamino)-2-((3,5-dimethylphenylimino)methyl)phenol (L3), 2-((2-chloro-4-methylphenylimino)methyl)-5-(diethylamino)phenol (L4), and 5-(diethylamino)-2-((2,6-diethylphenylimino)methyl)phenol (L5) were synthesized and characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopy. Three of the compounds (L1, L2, and L4) were analyzed by single crystal X-ray diffraction: L1 and L2 crystallized in orthorhombic P212121 and Pca21 space group, respectively, while L4 crystallized in monoclinic P21/c space group. Theoretical investigations were performed for all the synthesized compounds to evaluate the structural details. Drug-DNA interaction studies results from UV-Vis spectroscopy and electrochemistry complement that the compounds bind to DNA through electrostatic interactions. The cytotoxicity of the synthesized compounds was studied against cancer cell lines (HeLa and MCF-7) and a normal cell line (BHK-21) by means of an MTT assay compared to carboplatin, featuring IC50 values in the micromolar range. The pro-apoptotic mechanism for the active compound L5 was evaluated by fluorescence microscopy, cell cycle analysis, caspase-9 and -3 activity, reactive oxygen species production, and DNA binding studies that further strengthen the results of that L5 is a potent drug against cancer. Communicated by Ramaswamy H. Sarma.

2.
Chem Commun (Camb) ; 55(49): 7021-7024, 2019 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-31143911

RESUMO

DFT calculations were used to capture the properties of redox-switchable metal complexes relevant to the ring-opening polymerisation of cyclic esters by varying the metals, donors, linkers, and substituents in both accessible ferrocene oxidation states. A map of this chemical space highlights that modifying the ligand architecture and the metal has a larger impact on structural changes than changing the oxidation state of the ferrocene backbone.

3.
J Am Chem Soc ; 141(22): 9047-9062, 2019 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-31063359

RESUMO

Single-phase metal dodecaboride solid solutions, Zr0.5Y0.5B12 and Zr0.5U0.5B12, were prepared by arc melting from pure elements. The phase purity and composition were established by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and 10B and 11B solid-state nuclear magnetic resonance (NMR) spectroscopy. The effects of carbon addition to Zr1- xY xB12 were studied and it was found that carbon causes fast cooling and as a result rapid nucleation of grains, as well as "templating" and patterning effects of the surface morphology. The hardness of the Zr0.5Y0.5B12 phase is 47.6 ± 1.7 GPa at 0.49 N load, which is ∼17% higher than that of its parent compounds, ZrB12 and YB12, with hardness values of 41.6 ± 2.6 and 37.5 ± 4.3 GPa, respectively. The hardness of Zr0.5U0.5B12 is ∼54% higher than that of its UB12 parent. The dodecaborides were confirmed to be metallic by band structure calculations, diffuse reflectance UV-vis, and solid-state NMR spectroscopies. The nature of the dodecaboride colors-violet for ZrB12 and blue for YB12-can be attributed to charge-transfer. XPS indicates that the metals are in the following oxidation states: Y3+, Zr4+, and U5+/6+. The superconducting transition temperatures ( Tc) of the dodecaborides were determined to be 4.5 and 6.0 K for YB12 and ZrB12, respectively, as shown by resistivity and superconducting quantum interference device (SQUID) measurements. The Tc of the Zr0.5Y0.5B12 solid solution was suppressed to 2.5 K.

4.
Chem Commun (Camb) ; 55(39): 5587-5590, 2019 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-31020301

RESUMO

The synthesis of (thiolfan*)Zr(NEt2)2 (thiolfan* = 1,1'-bis(2,4-di-tert-butyl-6-thiophenoxy)ferrocene) and its catalytic activity for intramolecular hydroamination are reported. In situ oxidation and reduction of the metal complex results in reactivity towards different substrates. The reduced form of (thiolfan*)Zr(NEt2)2 catalyzes hydroamination reactions of primary aminoalkenes, whereas the oxidized form catalyzes hydroamination reactions of secondary aminoalkenes.

5.
Acc Chem Res ; 52(2): 415-424, 2019 02 19.
Artigo em Inglês | MEDLINE | ID: mdl-30707548

RESUMO

Switchable catalysts incorporate stimuli-responsive features and allow synthetic tasks that are difficult or impossible to accomplish in other ways. They mimic biological processes in that they can provide both spatial and temporal control, unlike most reactions promoted by human-made catalysts that usually occur according to carefully optimized conditions. In the area of switchable catalysis, redox-switchable ring-opening polymerization (ROP) has attracted much attention, emerging as a powerful strategy for the development of environmentally friendly biodegradable copolymers, especially those containing blocks with complementary properties. Controlling the sequence and regularity of each copolymeric building block can affect the material properties significantly since they are directly related to the respective microstructures. Such control can be exerted with a well-designed redox-switchable catalyst by timing the oxidation and reduction events. In highly selective systems, one form of the catalyst reacts with a monomer until the redox state of the catalyst is altered, at which point the altered state of the catalyst reacts with another monomer. The reaction time may be varied from one cycle to another to generate various designer multiblock copolymers. The first instance of redox-mediated ROP was described by N. Long and co-workers in 2006. This example, as well as many early reported redox-switchable catalysts, could only achieve an on/off switch of activity toward a single monomer or substrate. However, our efforts brought on a general strategy for designing redox-switchable metal complexes that can catalyze different reactions in two oxidation states. In recent years, our contributions to this research field led to the synthesis of several multiblock copolymers prepared from biorenewable resources. This Account provides an overview of reported redox-switchable polymerization catalysts that allow for complementary reactivity in different oxidation states and highlights the potential of this strategy in preparing biodegradable materials. First, we define the field of redox-switchable catalysis and illustrate the design and significance of our ferrocene-chelating ligands, in which the oxidation state of iron in ferrocene can control the reactivity of the resulting metal complexes remotely. Next, we illustrate recent advances in the synthesis of new biodegradable copolymers including (1) how to tune the activity of the ROP catalysts by exploring various metal centers and ferrocene-based ligand combinations; (2) how to synthesize new multiblock copolymers of cyclic esters, epoxides, and carbonates by redox-switchable ROP; and (3) how to understand the mechanism of these reactions by discussing both experimental and theoretical investigations. By the application and development of redox-switchable strategies, various novel materials and reactions can be expected in the future.

6.
Dalton Trans ; 48(9): 2996-3002, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30747193

RESUMO

A zirconium compound, (salfen)Zr(OiPr)2 (salfen = N,N'-bis(2,4-di-tert-butylphenoxy)-1,1'-ferrocenediimine), was tested as a redox switchable catalyst for the ring opening polymerization of cyclic esters and epoxides. Different activities were observed in the reduced and oxidized state, and an orthogonal switch on monomer activities could be achieved. Diblock and triblock copolymers were synthesized using an in situ redox switch of the catalyst oxidation state.

7.
iScience ; 7: 120-131, 2018 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-30267674

RESUMO

Neutral zinc alkoxide complexes show high activity toward the ring-opening polymerization of cyclic esters and carbonates, to generate biodegradable plastics applicable in several areas. Herein, we use a ferrocene-chelating heteroscorpionate complex in redox-switchable polymerization reactions, and we show that it is a moderately active catalyst for the ring-opening polymerization of L-lactide, ɛ-caprolactone, trimethylene carbonate, and δ-valerolactone. Uniquely for this type of catalyst, the oxidized complex has a similar polymerization activity as the corresponding reduced compound, but displays significantly different rates of reaction in the case of trimethylene carbonate and δ-valerolactone. Investigations of the oxidized compound suggest the presence of an organic radical rather than an Fe(III) complex. Electronic structure and density functional theory (DFT) calculations were performed to support the proposed electronic states of the catalytic complex and to help explain the observed reactivity differences. The catalyst was also compared with a monomeric phenoxide complex to show the influence of the phosphine-zinc interaction on catalytic properties.

8.
Chem Sci ; 9(8): 2168-2178, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-29719690

RESUMO

Poly(l-lactide) (PLA) is a bioderived and biodegradable polymer that has limited applications due to its hard and brittle nature. Incorporation of 1,3-trimethylene carbonate into PLA, in a block copolymer fashion, improves the mechanical properties, while retaining the biodegradability of the polymer, and broadens its range of applications. However, the preparation of 1,3-trimethylene carbonate (TMC)/l-lactide (LA) copolymers beyond diblock and triblock structures has not been reported, with explanations focusing mostly on thermodynamic reasons that impede the copolymerization of TMC after lactide. We discuss the preparation of multiblock copolymers via the ring opening polymerization (ROP) of LA and TMC, in a step-wise addition, by a ferrocene-chelating heteroscorpionate zinc complex, {[fc(PPh2)(BH[(3,5-Me)2pz]2)]Zn(µ-OCH2Ph)}2 ([(fcP,B)Zn(µ-OCH2Ph)]2, fc = 1,1'-ferrocenediyl, pz = pyrazole). The synthesis of up to pentablock copolymers, from various combinations of LA and TMC, was accomplished and the physical, thermal, and mechanical properties of the resulting copolymers evaluated.

9.
J Am Chem Soc ; 139(29): 9807-9810, 2017 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-28683547

RESUMO

Herein, we present the intramolecular [2+2] cycloadditions of dienones promoted through sensitization, using a polypyridyl iridium(III) catalyst, to form bridged cyclobutanes. In contrast to previous examples of straight [2+2] cycloadditions, these efficient crossed additions were achieved under irradiation with visible light. The reactions delivered desired bridged benzobicycloheptanone products with excellent regioselectivity in high yields (up to 96%). This process is superior to previous syntheses of benzobicyclo[3.1.1]heptanones, which are readily converted to B-norbenzomorphan analogues of biological significance. Electrochemical, computational, and spectroscopic studies substantiated the mechanism of triplet energy transfer and explained the unusual regiocontrol.


Assuntos
Reação de Cicloadição , Ciclobutanos/síntese química , Transferência de Energia/efeitos da radiação , Cetonas/química , Luz , Processos Fotoquímicos , Catálise , Ciclobutanos/química , Irídio/química , Estrutura Molecular
10.
Inorg Chem ; 56(3): 1375-1385, 2017 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-28103034

RESUMO

The impact of the metal size and Lewis acidity on the polymerization activity of group 13 metal complexes was studied, and it was shown that, within the same ligand family, indium complexes are far more reactive and selective than their gallium analogues. To this end, gallium and aluminum complexes supported by a tridentate diaminophenolate ligand, as well as gallium complexes supported by N,N'-ethylenebis(salicylimine)(salen) ligands, were synthesized and compared to their indium analogues. Using the tridentate ligand set, it was possible to isolate the gallium chloride complexes 3 and (±)-4 and the aluminum analogues 5 and (±)-6. The alkoxygallium complex (±)-2, supported by a salen ligand, was also prepared and characterized and, along with the three-component system GaCl3/BnOH/NEt3, was tested for the ring-opening polymerization of lactide and ε-caprolactone. The polymerization rates and selectivities of both systems were significantly lower than those for the indium analogues. The reaction of (±)-2 with 1 equiv of lactide forms the first insertion product, which is stable in solution and can be characterized at room temperature. In order to understand the differences of the reactivity within the group 13 metal complexes, a Lewis acidity study using triethylphosphine oxide (the Gutmann-Beckett method) was undertaken for a series of aluminum, gallium, and indium halide complexes; this study shows that indium halide complexes are less Lewis acidic than their aluminum and gallium analogues. Density functional theory calculations show that the Mulliken charges for the indium complexes are higher than those for the gallium analogues. These data suggest that the impact of ligands on the reactivity is more significant than that of the metal Lewis acidity.

11.
J Am Chem Soc ; 139(4): 1420-1423, 2017 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-28075128

RESUMO

DyIII single-ion magnets (SIMs) with strong axial donors and weak equatorial ligands are attractive model systems with which to harness the maximum magnetic anisotropy of DyIII ions. Utilizing a rigid ferrocene diamide ligand (NNTBS), a DyIII SIM, (NNTBS)DyI(THF)2, 1-Dy (NNTBS = fc(NHSitBuMe2)2, fc = 1,1'-ferrocenediyl), composed of a near linear arrangement of donor atoms, exhibits a large energy barrier to spin reversal (770.8 K) and magnetic blocking (14 K). The effects of the transverse ligands on the magnetic and electronic structure of 1-Dy were investigated through ab initio methods, eliciting significant magnetic axiality, even in the fourth Kramers doublet, thus demonstrating the potential of rigid diamide ligands in the design of new SIMs with defined magnetic axiality.

12.
Inorg Chem ; 55(20): 10013-10023, 2016 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-27494712

RESUMO

Our group has focused on the organometallic chemistry of rare-earth metals and actinides for a decade. By installing ferrocenediamide ligands at electropositive metal centers, we have been able to disclose unprecedented reactivity toward aromatic N-heterocycles, arenes, and other small molecules such as P4. Systematic studies employing X-ray crystallography, spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the ferrocene backbone could stabilize the electron-deficient metal through a donor-acceptor-type interaction. Most noteworthy is that this interaction can be readily turned on or off by the addition or removal of a Lewis base. In addition to its flexible coordination, the redox-active nature of the ferrocene backbone enabled us to explore redox-switchable transformations. The introduction of ferrocene-based ligands into organolanthanide chemistry not only helped us to study intriguing fundamental problems but also led to fruitful chemistry including small-molecule activation and controlled copolymerization reactions.

13.
Dalton Trans ; 44(35): 15360-71, 2015 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-26247323

RESUMO

Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes.

14.
Chem Commun (Camb) ; 51(47): 9643-6, 2015 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-25973852

RESUMO

An indium complex supported by a ferrocene-derived Schiff base ligand has an unprecedented high activity toward ε-caprolactone, δ-valerolactone, and ß-butyrolactone. l-Lactide, d,l-lactide, and trimethylene carbonate polymerizations also showed moderate to high activity.


Assuntos
Ésteres/química , Compostos Ferrosos/química , Índio/química , Compostos Organometálicos/química , Óxidos/química , Polimerização , 4-Butirolactona/análogos & derivados , 4-Butirolactona/química , Caproatos/química , Ciclização , Dioxanos/química , Ácido Láctico/química , Lactonas/química , Metalocenos , Pironas/química , Bases de Schiff/química , Estereoisomerismo
15.
Inorg Chem ; 54(5): 2374-82, 2015 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-25695369

RESUMO

Inverse sandwich biphenyl complexes [(NN(TBS))Ln]2(µ-biphenyl)[K(solvent)]2 [NN(TBS) = 1,1'-fc(NSi(t)BuMe2)2; Ln = Gd, Dy, Er; solvent = Et2O, toluene; 18-crown-6], containing a quadruply reduced biphenyl ligand, were synthesized and their magnetic properties measured. One of the dysprosium biphenyl complexes was found to exhibit antiferromagnetic coupling and single-molecule-magnet behavior with Ueff of 34 K under zero applied field. The solvent coordinated to potassium affected drastically the nature of the magnetic interaction, with the other dysprosium complex showing ferromagnetic coupling. Ab initio calculations were performed to understand the nature of magnetic coupling between the two lanthanide ions bridged by the anionic arene ligand and the origin of single-molecule-magnet behavior.

16.
Inorg Chem ; 54(4): 1778-84, 2015 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-25607817

RESUMO

The first example of a ferrocene-chelating heteroscorpionate, [Li(THF)2][fc(PPh2)(BH[(3,5-Me)2pz]2)] ((fc(P,B))Li(THF)2, fc = 1,1'-ferrocenediyl) is described. Starting from a previously reported compound, fcBr(PPh2), a series of ferrocene derivatives, fc(PPh2)(B[OMe]2), [Li(OEt2)][fc(PPh2)(BH3)], [Li(THF)2][fc(PPh2)(BH[(3,5-Me)2pz]2)] (pz = pyrazole), was isolated and characterized. Compound (fc(P,B))Li(THF)2 allowed the synthesis of the corresponding nickel and zinc complexes, (fc(P,B))NiCl, (fc(P,B))NiMe, (fc(P,B))ZnCl, and (fc(P,B))ZnMe. All compounds were characterized by NMR spectroscopy, while the zinc and nickel complexes were also characterized by X-ray crystallography. The redox behavior of (fc(P,B))NiCl, (fc(P,B))NiMe, (fc(P,B))ZnCl, and (fc(P,B))ZnMe was studied by cyclic voltammetry and supported by density functional theory calculations.

17.
Dalton Trans ; 44(6): 2676-83, 2015 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-25510329

RESUMO

The synthesis and characterization of (bipy)(2)U(N[t-Bu]Ar)(2) (1-(bipy)(2), bipy = 2,2'-bipyridyl, Ar = 3,5-C(6)H(3)Me(2)), (bipy)U(N[(1)Ad]Ar)(3) (2-bipy), (bipy)(2)U(NC[t-Bu]Mes)(3) (3-(bipy)(2), Mes = 2,4,6-C(6)H(2)Me(3)), and IU(bipy)(NC[t-Bu]Mes)(3) (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)(2) and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)(2), one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4'-dimethyl-2,2'-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state.


Assuntos
2,2'-Dipiridil/química , Amidas/química , Iminas/química , Compostos Organometálicos/química , Urânio/química , Ânions/química , Cristalografia por Raios X , Ligantes , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , Compostos Organometálicos/síntese química
18.
J Am Chem Soc ; 136(50): 17410-3, 2014 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-25431837

RESUMO

A new type of C-H bond activation mediated by rare-earth metals under reducing conditions is reported. The synergy between reductants and rare-earth-metal complexes allows the cleavage of unactivated aromatic C-H bonds. The reaction between rare-earth-metal iodides supported by a 1,1'-ferrocenediamide ligand and potassium graphite in benzene leads to the formation of a 1:1 metal molar ratio of the corresponding metal hydride and metal phenyl complex. A proposed mechanism involving an inverse sandwich arene bimetallic intermediate is supported by experimental and computational studies.

19.
J Am Chem Soc ; 136(32): 11264-7, 2014 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-25062499

RESUMO

The activity of several group 4 metal alkoxide complexes supported by ferrocene-based ligands was controlled using redox reagents during the ring-opening polymerization of l-lactide and ε-caprolactone. Switching in situ between the oxidized and reduced forms of a metal complex resulted in a change in the corresponding rate of polymerization. Opposite behavior was observed for each monomer used. One-pot copolymerization of the two monomers to give block copolymers was also achieved.

20.
Chem Commun (Camb) ; 50(40): 5221-3, 2014 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-24343705

RESUMO

Group 3 metal (E)-stilbene complexes supported by a ferrocene diamide ligand were synthesized and characterized. Reactivity studies showed that they behave similar to analogous naphthalene complexes. Experimental and computational results indicated that the double bond was reduced and not a phenyl ring, in contrast to a previously reported uranium (E)-stilbene complex.

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