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(Graph Presented). A three-dimensional metal-organic framework (1) with fourfold interpenetrating diamondoid networks was constructed using a macrocyclic nickel(II) complex and a tetracarboxylic ligand 4,4?,4?,4-(cyclohexane-1,2-diyibis(azanetriyl))tetrakis(methylene)tetrabenzoic acid as building blocks. Despite the fourfold interpenetration, 1 possesses one-dimensional channels that are occupied by water and CH3CN guest molecules. Once the guest molecules were removed, the framework and pores in desolvated 1 are dynamic with large adsorption hysteresis loops, which exhibit selective gas adsorption for CO2 at 195 K over N2 and H2 at 77 K and selective adsorption for methanol, ethanol, and n-propanol over isopropanol at 298 K.

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

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New macrocyclic chiral Mn(III) salen complexes (C1-C4) were synthesized and were used as catalysts for oxidative kinetic resolution (OKR) of secondary alcohols with diacetoxyiodobenzene (PhI(OAc)2) and N-bromosuccinimide (NBS), in biphasic dichloromethane: water solvent mixture. Good to excellent enantioselectivities were achieved with catalyst C2 for several secondary alcohols having different steric environment. In general with catalyst C2, NBS as a co-oxidant showed better enantioselectivity than PhI(OAc)2 in OKR. The catalyst C2 was easily retrieved from the reaction mixture by the addition of hexane and recycled seven times both with NBS and PhI(OAc) 2 as co-oxidants without losing its performance. Based on the experimental results a mechanism for OKR of racemic 1-phenylethanol has been proposed where (R,R)-Mn-salen preferably binds with (S)-1-phenylethanol to give (R)-1-phenylethanol in excess at the end of the reaction.

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Metal catalyst and ligand design,
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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 20439-47-8, name is (1R,2R)-Cyclohexane-1,2-diamine, introducing its new discovery. Formula: C6H14N2

Reaction of RuHCl(PPh3)2(diamine) (1a, diamine = (R,R)-1,2-diaminocyclohexane, (R,R)-dach; 1b, diamine = ethylenediamine, en) with KOtBu in benzene quickly generates solutions of the amido-amine complexes RuH(PPh3)2(NHC6H10NH 2), (2a?), and RuH(PPh3)2(NHCH 2CH2NH2), (2b?), respectively. These solutions react with dihydrogen to first produce the trans-dihydrides (OC-6-22)-Ru(H)2(PPh3)2(diamine) (t,c-3a, t,c-3b). Cold solutions (-20C) containing trans-dihydride t,c-3a react with acetophenone under Ar to give (S)-1-phenylethanol (63% ee). Complexes t,c-3 have lifetimes of less than 10 min at 20 and then isomerize to the cis-dihydride, cis-bisphosphine isomers (OC-6-32)-Ru(H)2(PPh 3)2(diamine) (Delta/Lambda-c,c-3a, c,c-3b). A solution containing mainly Delta/Lambda-c,c-3a reacts with acetophenone under Ar to give (S)-1-phenylethanol in 20% ee, whereas it is an active precatalyst for its hydrogenation under 5 atm H2 to give 1-phenylethanol with an ee of 50-60%. Complexes c,c-3 isomerize to the cis-dihydride, trans-bisphosphine complexes (OC-6-13)-Ru(H)2(PPh3)2(diamine) (c,t-3a, c,t-3b) with half-lives of 40 min and 1 h, respectively. A mixture of Delta/Lambda-c,c-3a and c,f-3a can also be obtained by reaction of 1a with KBH(Busec)3. A solution of complex c,t-3a in benzene under Ar reacts very slowly with acetophenone. These results indicate that the trans-dihydrides t,c-3a or t,c-3b along with the corresponding amido-amine complexes 2a? or 2b? are the active hydrogenation catalysts in benzene, while the cis-dihydrides c,c-3a or c,c-3b serve as precatalysts. The complexes RuCl2(PPh3)2((R,R)-dach) or 1a, when activated by KOtBu, are also sources of the active catalysts. A study of the kinetics of the hydrogenation of acetophenone in benzene catalyzed by 3a indicates a rate law: rate = k[c,c-3a]initial[H2] with k = 7.5 M-1 s-1. The turnover-limiting step appears to be the reaction of 2a? with dihydrogen as it is for RuH(NHCMe 2CMe2NH2)(PPh3)2 (2c?). The catalysts are more active in 2-propanol, even without added base, and the kinetic behavior is complicated. The basic cis-dihydride c,t-3a reacts with [NEt3H]BPh4 to produce the dihydrogen complex (OC-14)-[Ru(eta2-H2)(H)(PPh3) 2-((R,R)-dach)]BPh4 (4) and with diphenylphosphinic acid to give the complex RuH(O2PPh2)(PPh3) 2((R,R)-dach) (5). The structure of 5 models aspects of the transition state structure for the ketone hydrogenation step. Complex 2b? decomposes rapidly under Ar to give dihydrides 3b along with a dinuclear complex (PPh3)2HRu(mu-eta2;eta4- NHCHCHNH)RuH(PPh3)2 (6) containing a rare, bridging 1,4-diazabutadiene group. The formation of an imine by beta-hydride elimination from the amido-amine ligand of 2a? under Ar might explain some loss of enantioselectivity of the catalyst. The structures of complexes 1a, 5, and 6 have been determined by single-crystal X-ray diffraction.

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

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The disclosure includes hydroxamic compounds of Formula I: (I) wherein P, Z, and m are defined herein. Also disclosed is a method for treating a neoplastic disease or an immune disease with these compounds.

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

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The crystal structures of the diastereomeric salt pair, Lambda-lel3-(d-tart)*3H2O (1) and Lambda-lel3-(d-tart)*5H2O (2) (chxn=trans-1,2-cyclohexanediamine and d-tart=(+)-(R,R)-tartrate dianion), have been determined by a single-crystal X-ray diffraction techniques.Crystal 1 is orthorhombic with the space group P212121, a=10.093(2), b=13.589(4), c=22.011(4) Angstroem, and Z=4.Crystal 2 is also orthorhombic with the same space group, a=11.197(2), b=13.102(2), c=22.402(2) Angstroem, and Z=4.In 1, the d-tart ion makes a familiar face-to-face contact with the Lambda complex, in which the two alcoholic and one carboxylic O atoms of the d-tart ion are involved in the multiple hydrogen bonds to the three H-N groups on the triangular face of the complex.This contact mode resembles the one found earlier in the chloride d-tart salt of the corresponding Lambda Co(III) complex, Lambda-lel3-Cl(d-tart)*2H2O (3).On the other hand, no such face-to-face contact is present in 2, though it has been found in the corresponding Lambda Co(III) complex, Lambda-lel3-Cl(d-tart)*2H2O (4) in which the d-tart ion is obliged to rotate the distal carboxylato group so as to avoid the steric repulsion otherwise imposed on it by one of the bulky chxn ligands.Detailed comparison of the above four crystal structures revealed that the packing modes of the respective complex cations and couterions are surprisingly similar to one another, indicating that the absence of such a face-to-face contact in 2 is attributed to the weaker affinity of the d-tart ion for the divalent Lambda Ni(II) complex, rather than to the steric demands of the crystal packing in 2.In 2 are found two deformed contact modes similar to each other, in which the d-tart ion directs its three O atoms to the triangular face, but only one of them is hydrogen-bonded to one or two of the three H-N groups on the triangular face.The d-tart ion thereby avoids the steric repulsion that would be imposed on it if it should make a usual face-to-face contact with the Lambda complex.

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

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New chiral chelating C2 bis-oxazoline-amide ligands (1) exhibiting a highly flexible molecular structure have been prepared in high yield through a versatile synthetic pathway. Combined crystallographic, variable temperature (VT)-NMR, IR, and ESI-MS studies have been carried out to investigate the nature of the 1-Pd complexes that are effective tools in controlling the stereochemical outcome of Pd-catalyzed allylic alkylations (ee up to 98%).

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

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Mono- and dinuclear oxidorhenium(V) complexes with hemiacetal ligands were isolated from a reaction of (NBu4)[ReOCl4] with a potentially tetradentate Schiff base prepared from (1R,2R)-cyclohexane-1, 2-diamine and (2-formylphenyl)diphenylphosphine in methanol. The hemiacetal is formed by solvolysis of first one imine functionality of the Schiff base, whereas the second remains intact. The resulting amine/iminophosphine coordinates as a tridentate N,N, P ligand in a dinuclear compound. Ongoing degradation of the Schiff base gives more hemiacetal (HL1a) and the final product, the monomeric complex [ReOCl(L1a)2] is formed. Cleavage of the organic framework is not observed during the reaction of (NBu4)[ReOCl4] with a related Schiff base derived from ethylene-1, 2-diamine and (2-formylphenyl)diphenylphosphine. The Schiff base reacts as a bis-bidentate N, P ligand and a dinuclear oxorhenium(V) compound with a central ethylene bridge is formed. Copyright

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

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An optically active sulfimide compound is produced by using a specified Ru(salen)(CO) complex as a catalyst and subjecting a specified alkyl aryl sulfide compound to an asymmetric sulfimidation with a specified azide compound having an easily eliminating group.

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

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The present invention relates to 3,4,5,6-tetrahydrophthalamide derivatives and 3,4,5,6-tetrahydroisophthalimide derivatives having excellent effects as effective active ingredients of herbicides, and processes for preparing the same, and provides the compounds having a more efficient herbicidal activity, and efficient and industrial processes for the preparation thereof. More specifically, the tetrahydrophthalimide derivative obtained by reacting a halogen-substituted 5-cycloalkyloxyaniline derivative with a 3,4,5,6-tetrahydrophthalic anhydride, or the tetrahydroisophthalimide derivative of the present invention is reacted with various types of amines to prepare a tetrahydrophthalamide derivative represented by the general formula (I): STR1 These tetrahydrophthalamide derivatives and the tetrahydroisophthalimide derivatives exhibit excellent herbicidal activities in the soil treatment in the paddy field and field and the stem-foliar treatment. The tetrahydroisophthalimide derivatives are also useful as intermediates for the preparation of the tetrahydrophthalamide derivatives, etc.

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

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An optically active lactone compound is produced by using a Zr(salen) complex of the following formula (I) or its enantiomer as a catalyst and subjecting a cyclic ketone compound to a Baeyer-Villiger reaction with at least one oxidizer selected from hydrogen peroxide, aqueous hydrogen peroxide and urea-hydrogen peroxide adduct in a solvent: 1wherein Ar1 is an aryl group having a carbon number of 10 to 16 and Y is a phenoxy group or an alkoxy group having a carbon number of 1 to 10.

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