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Racemic and enantiomerically pure titanium(IV) complexes with ortho-bromo-para-methyl-substituted diaminobis(phenolato) ligands were prepared with NH-, NMe-, and bipyrrolidine-based diamino bridges through ligand-to-metal chiral induction. The hydrolytic stability of the complexes was evaluated, and their cytotoxicity was measured using HT-29 human colon cancer cells based on the MTT assay. All stereochemical forms of the NMe-based complexes, although demonstrating the highest hydrolytic stability, were biologically inactive. For the NH and bipyrrolidine-based active complexes, the pure enantiomers exhibited high cytotoxicity whereas the racemic mixtures were inactive, supporting the involvement of a polynuclear active species. The bipyrrolidine complexes appear to provide the best combination of hydrolytic stability and biological activity, presumably by minimizing steric bulk and consequently enabling biological accessibility. Racemic and optically pure phenolato titanium(IV) complexes were prepared with NH, NMe, and bipyrrolidine-based diamino bridges. The optically pure bipyrrolidine complexes provide the best combination of hydrolytic stability and biological activity, presumably by maintaining small enough steric bulk to enable biological accessibility.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The condensation of enantiopure (1R,2R)-(-)-1,2-diaminocyclohexane with two equivalents of 2,2,-bipyridine-6-carbaldehyde followed by reduction with NaBH4 allows the facile synthesis of the enantiopure hexadentate ligand (R,R)-3. Each, tridentate metal-binding domain in (R,R)-3 exhibits a degree of flexibility arising from inversion at the amine nitrogen centre and rotation, about N-C and C-C single bonds. This leads to the formation of either M-[Mf(R,R)-3}]2+ or P[M((R,R)-3}]2+. The solid-state structures of the copper(II), iron(II) and zinc(II) complexes of (R,R)-3 all show a preference for M-[M((R,R)-3}]2+. In solution, [Fe{(R,R)-3}]2+ exists predominantly as one diastereoisomer (assumed to be the Mform). The preference for the M- over P-form is rationalizedss in terms of a favourable anti configuration of the NH and cyclohexane-1,2-diyl CH hydrogen atoms in the M-form, and an unfavourable syn-configuration in the P-form. When (R,R)-4, the Schiff base analogue of (R,R)-3, combines with zinc(II) or silver(I), [2+2] double helicates with M-chirality assemble in the solid state. With (S,S)-4, iron(II) also assembles into a dinuclear, double helicate with M-handedness. Complete stereoselectivity is observed in solution with NMR spectroscopic data indicating the presence of one diastereoisomer. The preference for a dinuclear over mononuclear helicate can be traced to a decrease in ligand flexibility on going from 3 (saturated backbone) to 4 (unsaturated imine backbone).

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Oxovanadium(V) complexes, VVO (Schiff base)Y (Y=ClO4, Cl, NO3), with quadridentate Schiff base ligands derived from optically active 1,2-diamines and salicylaldehyde or its derivatives were prepared by oxidizing the corresponding VIVO (Schiff base) with CeIV in acetonitrile followed by the addition of HY.The complexes were characterized by their 1H NMR, IR, UV-Vis, and circular dichroism spectra, and electrochemistry.Reversible reduction potentials (V5+/V4+) obtained by cyclic voltammetry for a series of oxovanadium(V) complexes with Schiff base ligands derived from 5-substituted salicylaldehydes showed a linear dependence on the Hammett parameter.Both the vanadium(IV) and the vanadium(V) complexes catalyze asymmetric oxidation of sulfides into the corresponding sulfoxides with organic hydroperoxides.The oxovanadium(IV) complex catalysts gave much better asymmetric induction than the oxovanadium(V) complex catalysts and in most cases the enantiomeric excess (ee) ranged between 20 and 40percent.In the reaction of VIVO (Schiff base) with an organic hydroperoxide the complex is finally converted into the oxovanadium(V) species, and a dark brown intermediate is suggested to be the catalytically active species.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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There is a need for fast detection methods for the banned rodenticide tetramethylenedisulfotetramine (TETS), a highly potent blocker of the gamma-aminobutyric acid (GABAA) receptors. General synthetic approach toward two groups of analogues was developed. Screening of the resulting library of compounds by FLIPR or whole-cell voltage-clamp revealed that, despite the structural differences, some of the TETS analogues retained GABAA receptor inhibition; however, their potency was an order of magnitude lower. Antibodies raised in rabbits against some of the TETS analogues conjugated to protein recognized free TETS and will be used for the development of an immunoassay for TETS.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A series of new photoluminescent hemidisc-shaped NiII Schiff-base complexes has been synthesized. The ligands and their complexes were characterized by FTIR and 1H and 13C NMR spectroscopy, FAB-MS and elemental analysis. The mesomorphic behaviour of the ligands and their complexes was probed by polarizing optical microscopy and differential scanning calorimetry. The molecular organization in the mesophase was determined by X-ray diffraction techniques. The ligands are nonmesogenic but their complexes exhibited thermally stable rectangular columnar (Colr) mesophases at about 227 C. The complexes are blue-light emitters in solution (ca. 434 nm, Phi = 19%) and in the solid state (ca. 469 nm, Phi = 7%) at lambdaex = 350 nm. A DFT study was carried out using DMol3 at the BLYP/DNP level to obtain a stable, optimized structure, which revealed a distorted square-planar geometry for the nickel complexes.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Asymmetric Diels-Alder reactions of 1,4-naphthoquinone and 2-acetyl-1,4-naphthoquinone with cyclopentadiene catalyzed by bis(oxazoline)-metal complexes afforded the corresponding Diels-Alder adducts. Moderate levels of enantiomeric excess were obtained and a number of different reaction conditions evaluated.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The monofunctional platinum complex cis-[Pt(NH3) 2Cl(Am)]+, also known as phenanthriplatin, where Am is the N-heterocyclic base phenanthridine, has promising anticancer activity. Unlike bifunctional compounds such as cisplatin, phenanthriplatin can form only one covalent bond to DNA. Another distinguishing feature is that phenanthriplatin is chiral. Rotation about the Pt-N bond of the phenanthridine ligand racemizes the complex, and the question arises as to whether this process is sufficiently slow under physiological conditions to impact its DNA-binding properties. Here we present the results of NMR spectroscopic, X-ray crystallographic, molecular dynamics, and density functional theoretical investigations of diastereomeric phenanthriplatin analogs in order to probe the internal dynamics of phenanthriplatin. These results reveal that phenanthriplatin rapidly racemizes under physiological conditions. The information also facilitated the interpretation of the NMR spectra of small molecule models of phenanthriplatin-platinated DNA. These studies indicate, inter alia, that one diastereomeric form of the complexes cis-[Pt(NH3)2(Am)(R- Gua)]2+, where R-Gua is 9-methyl- or 9-ethylguanine, is preferred over the other, the origin of which stems from an intramolecular interaction between the carbonyl oxygen of the platinated guanine base and a cis-coordinated ammine. The relevance of this finding to the DNA-damaging properties of phenanthriplatin and its biological activity is discussed.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A series of saccharide-derived bifunctional tertiary amine-thioureas for the asymmetric Michael addition reaction have been designed and synthesized. The addition products between malonates and various nitroolefins were obtained in high yields (up to 99%) and excellent enantioselectivities (up to 99% ee). Georg Thieme Verlag Stuttgart.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Polymerizable gelator 1 which has two diacetylene groups as well as two amide groups showed an excellent gelation ability for many organic solvents. Photoirradiation readily induced polymerization in the gel phase but the polymerization results were dependent upon the gelation solvent. It was shown that the three-dimensional cross-link of these organic gels resulted in new robust gels, retaining their gel fiber super-structure.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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With benzyl group as a linker, trans-(1R,2R)-diaminocyclohexane was incorporated into the framework of mesoporous silica through one-step co-condensation of tetramethoxysilane with N,N?-bis[4-(trimethoxysilyl) benzyl]-(-)-(1R,2R)-diaminocyclohexane using cetyltrimethylammonium bromide as a structure-directing agent under basic conditions. All materials were fully characterized by X-ray diffraction, N2 sorption isotherms, transmission electron microscopy, and 13C and 29Si cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy. Coordinated with [Rh(cod)Cl]2, the material exhibited a TOF up to ?414 h-1 with 30% ee for the asymmetric transfer hydrogenation of acetophenone. Various ketones were hydrogenated with different activities and enantioselectivities. An enantioselectivity of about 61% ee was observed in the case of 2-acetylnaphthalene. Moreover, a comparison of the catalytic properties of the materials with benzyl and propyl groups as linkers indicates the importance of the rigidity and electron-withdrawing ability of the linker in the high reaction rate of the catalysts.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI