Synthesis and Characterization of Chiral Organogallium and Indium Complexes with Salen Ligands

Several new chiral organogallium and indium complexes with chiral Salen (1 and 2) as anxciliary ligands have been synthesized and characterized by elemental analysis, IR, 1H NMR and Mass spectroscopy. For the gallium, mono and bimetallic complexes were obtained, whereas ring closure complexes of indium were obtained.

Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl

Two homochiral mercury （1） and cadmium （2） complexes derived from chiral twisted biphenyl pyridine ligand （3,3＇-bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl） have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038（16）, b = 14.3630（17）, c = 7.0257（8）, V = 1433.3（3）3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F（000） = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ（I）. For 2, a = 14.212（3）, b = 14.392（3）, c = 7.0498（14）, V = 1442.0（5）3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F（000） = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ（I）. The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.

Novel Chiral PNNP-Ru Complexes:Synthesis and Application in Asymmetric Transfer Hydrogenation of Ketones

The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities（up to 99% conversion） and excellent enantioselectivities（up to 96% e.e.） under mild conditions. The chiral ruthenium（Ⅱ） complex （R,R）-3 has been prepared and characterized by NMR and X-ray crystallography.

Synthesis and Catalytic Activity of Nickel(Ⅱ)and Cobalt(Ⅱ) Complexes Involving Chiral Leucinol

The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.

Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one

Synthesized and characterized new chiral palladium complexes, some of which contain asymmetric donor nitrogen atom. Nitrogen-containing derivatives (+) - and (-)-2α-hydroxypinan-3-one- (1R,2R,5R)-3-(benzylimino)-2,6,6-trimethylbicy- clo[3.1.1]heptane-2-ol (HL1), (1S,2S,3S,5S)-3- (benzylamino)-2,6, 6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL2), (1R,2R,5R)-3-((S)-α-methyl- benzylimino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL3), (1R,2R,3R,5R)-3-((S)-α-methyl- benzylamino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL4) -were studied as optically active ligands.

Synthesis of Chiral Schiff Base Metal Complex Inducing CD and Elucidation of Structure of Adsorption on Surface of Gold Nanoparticles

We have prepared supramolecular systems of chiral Schiff base Ni(II), Cu(II), Zn(II) complexes and colloidal gold nanoparticles (AuNP) of 10 nm diameters. They demonstrated that direct adsorption of chiral Schiff base metal complex on the surface of AuNP owing to observation of clear induced CD spectra for the first time. We observed and discussed induced CD bands on AuNP from chiral Schiff base Ni(II), Cu(II), Zn(II) complexes.

Chiral Resolution of β-dl-Phenylalanine Using Chiral Macrocyclic Nickel(Ⅱ) Complexes

The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.

Resolution of Spiro[4.4]nonane-1,6-dione by Chiral Inclusion Complexation

The racemic spiro[4.4]nonane-1,6-dione was efficiently resolved through an enantioselective inclusion complexation using chiral host BINOL by simple recrystallization with 31 .9～38.4% yield and 1000%ee.

COPOLYMERIZATION PROCESS OF TRIPHENYLMETHYL METHACRYLATE AND MMA WITH CHIRAL ANIONIC COMPLEX INITIATOR

The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copolymer obtained in toluene possessed muchhigher specific rotation than that in THF. These copolymers have shown a tendency to a random and a like alternating structure, respectively.

Asymmetric Trimethylsilylcyanation of Benzaldebyde Catalyzed by Novel Ti(Ⅳ)-Chiral Schiff Base Complexes

Benzaldehyde has been trimethylsilylcyanated with a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. Cyanohydrin is obtalned in moderate e.e.values

THE ASYMMETRIC ALKYLATIONS OF CHIRAL TRANSITION METAL COMPLEXES OF(+)—CAMPHOR IMINE

The asymmetric alkylations of chiral transition metal complexes derived from (+)-camphor and 2-aminomethyl-6-methylpyridine were examined under mild conditions.The formation of the complexes 2 is conductive to the enhancement of di- astereoselectivity in the alkylations at room temperature.

Synthesis and CD Spectra of Chiral Molybdenum-fullerenyl Complexes with Pineno-bipyridine Ligands

The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inthe visible range show weak Cotton effects, which are approximately of mirror image, indicatingthat the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerenechromophores through the molybdenum centers and lead to induced CD effects.

SYNTHESIS OF CHIRAL MIXED-LICAND COMPLEXES AND THEIR USE IN ASYMMETRIC SYNTHESIS OF CHRYSANTHEMIC ACID

Several chiral mixed-ligand complexes have been synthesized and their efficiency as catalysts for the asymmetric synthesis of chrysanthemic acid tested.

Identification of Mosaic Order Area of Geometric Triangular Chiral Hexagonal Complexes in Interphase with Morphology Biosignature Pattern in the Interior of Martian Nested Impact Craters

From evolutionary miniaturization activation of ancestral larger genes stocks, an electromagnetic field derivate from cancer microscopic collision events participates in the elaboration of geometric complexes and chiral biomolecules that serve to build bodies with embryoid print as it develops during gestation. This miniaturization platform literally allows us to see what would otherwise remain completely invisible. In concordance with our observations collision extreme chaos generates in space time interval geometric scalable invariant extreme order. To determine whether our predictions are valid, we select Mars one of the planets with highest rate collision impact craters. The idea that impact events produce major geological effects that go far beyond the production of craters has recently been emphasized. We wonder if we could predict geometric chiral triangular hexagonal complexes in Martian landscape similar to those documented at microscopic, macroscopic, megascopic levels. We resolved to investigate the geomorphology patterns of more than 4000 collision impact craters in Mars landscape using images from Google Mars platforms, and HIRISE (High resolution imaging science experiment camera from the University of Arizona) based on a pattern recognition images algorithm we identified Mars mosaic order area (MOA). MOA is a circular cluster of overlap craters organized in apparent visible cycle sequential order oriented counterclockwise and consisting of nine craters that structure visible and measurable geometry in interface with biosignature morphologies in their interior not having been previously documented. Crater, therefore, is a step forward in understanding how collisions influence life, both on Earth and on other planets. We were pleased that the correctly pattern image algorithm predicted the identification of irreducible geometry matrix of GTCHC complexes in Martian impact craters. Cancer can inform astrobiology.

Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.