Enantioselective hydrogenation of acetophenone by(1S,2S)-DPEN-Ru(Ⅱ)Cl_2(PPh_3)_2 encapsulated in Al-MCM-41

<正>A chiral ruthenium complex[(1S,2S)-DPEN]-RuCl_2(PPh_3)_2(DPEN = 1,2-diphenylethylenediamine,PPh_3 = triphenylphosphine) was encapsulated in the channel of Al-MCM-41 by electrostatic adsorption and 1,1-dichlorosilacyclobutane modification.The prepared heterogeneous catalyst showed the same catalytic activity and enantioselectivity as the corresponding homogeneous catalyst in the asymmetric hydrogenation of acetophenone,and could be reused at least seven times without significant loss of catalytic activity and enantioselectivity.     

Identification of the starting reaction position in the hydrogenation of (N-ethyl)carbazole over Raney-Ni

Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rate-limiting step during the period, in which the conversion of carbazole was less than 40%. The hydrogenation process followed pseudo-first-order kinetics and the hydrogenation activation energies of carbazole and N-ethylcarbazole were 90 k J/mol and 115 k J/mol, respectively. The reaction starting position as well as the pathway of the hydrogenation of(N-ethyl)carbazole were investigated by comparing the kinetic characteristics of hydrogen uptake of carbazole and Nethylcarbazole. The results showed that the reaction was a stepwise hydrogenation process and the first H2 was added to the C1 = C10 double bond in the hydrogenation.     

Half-sandwich Ruthenium Complexes with Naphthalene-based Schiff Base Ligands: Syntheses,Characterization and Catalytic Activities for the Reduction of Nitroarenes

Three half-sandwich ruthenium(II) p-cymene complexes containing naphthalenebased Schiff base ligands [Ru(p-cymene)LCl](2 a~2 c) have been synthesized and characterized. Both Schiff-base ligands and ruthenium complexes were fully characterized by ~1H and ~(13)C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2 b was confirmed by single-crystal X-ray diffraction methods. For the complex: C_(24_H_(23)ClN_2ORu, M_r = 524.02, monoclinic, space group P21/c, a = 12.3888(4), b = 17.3296(6), c = 20.7744(7) ?, β = 92.8000(10)°, V = 4454.8(3) ?~3, Z = 8, Dc = 1.563 g/cm~3, μ = 0.936 mm~(-1), F(000) = 2128, S = 1.154, the final R = 0.0309 and w R = 0.0703. Moreover, these ruthenium complexes are active catalysts for the hydrogenation of nitroarenes to aromatic anilines in the presence of sodium tetrahydroborate(NaBH_4) reducing agent.     

SYNTHESIS AND STRUCTURE OF CU8S[S2P（OC2H5）2]6

<正> Cu8C24H60O12P6S13,Mt= 1651. 73,trigonal,R3,a=b = c= 12. 667(4) A,α= β=γ=111. 42(1)°.V=1441(2)A3,Z=1,Dc=1. 903g·cm-3,λ(MoKa) = 0. 71073 A ,μ(MoKa) = 35. 671cm-1, F ( 000 ) = 830, 293K. Final R = 0. 066,Rw= 0. 077 for 850 unique intensity data (I≥3σ(I)). Each unit cell of the crystal comprises of a neutral molecule of formula Cu8S(dtp)6[dtp=S2P(OEt)2],wherein the eight copper atoms are arranged at the corners of regular cube,with each dtp ligand μ4-bridged to each face of the cube and a μ8-S in the center bonded to all the eight copper atoms. Each copper atom is coordinated by four sulfur atoms in a tetrahedral configuration. The bond lengths of Cu-(μ8-S) are in the range of 2. 627(2)-2. 543(2) A ,those of Cu-S(dtp)in the range of 2. 251-2. 280A.The adjacent Cu-Cu bond lengths (2. 950(5)-3. 070(2) A) show a weak interaction between the copper atoms     

Synthesis of novel chiral tetraaza ligands and their application in enantioselective transfer hydrogenation of ketones

Novel chiral tetraaza ligands(R)-N,N′-bis[2-(piperidin-1-yl)benzylidene]propane-l,2-diamine 6 and(S)-N-[2-(piperidin-l- yl)benzylidene]-3-{[2-(piperidin-1-yl)benzylidene]amino}-alanine sodium salt 7 have been synthesized and fully characterized by NMR,IR,MS and CD spectra.The catalytic property of the ligands was investigated in Ir-catalyzed enantioselective transfer hydrogenation of ketones.The corresponding optical active alcohols were obtained with high yields and moderate ees under mild reaction conditions.     

Syntheses, Crystal Structures and Antibacterial Activities of Copper（Ⅱ） and Zinc（Ⅱ） Complexes Based on （E）-4-fluoro-2-（（3-morpholinopropylimino）methyl）phenol

Two Schiff base complexes [Cu(L)2] (1) and [Zn(L)2]·3H2O(2) of (E)-4-fluoro-2-((3-morpholino propylimino)methyl)phenol (HL) have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Crystal data for 1: triclinic, space group Pī with a=4.8000(10), b=11.109(2), c=13.921(3),α=66.55(3),β=80.35(3),γ=81.09(3)°, V=668.2(2)3 , Z=1, Dc=1.477g/cm 3 , F(000)=311, and the final R=0.0744 and wR=0.1601 for 2301 observed reflections with I > 2σ(I). And those for 2: monoclinic, space group P21 /c with a=14.789(3), b=11.713(2), c=18.846(4),β=107.85(3)°, V=3107.4(11)3 , Z=4, D c=1.389 g/cm 3 , F(000)=1368, and the final R=0.0749 and wR=0.1348 for 5423 observed reflections with I > 2σ(I). Both 1 and 2 are four-coordinated complexes, with a square-planar geometry of copper(Ⅱ) in 1 and a slightly distorted tetrahedral geometry of zinc(Ⅱ) in 2. An asymmetric unit consists of only one half of a Cu ion and one L ligand in 1, while an asymmetric unit is composed of one Zn ion, two L ligands and three water molecules in 2. Non-classical C-H···O and C-H F hydrogen bonds play important roles in the formation of a 1D chain of 1, but O-H O and O-H N hydrogen bonds play dominant roles in the self-assembly of a 3D network of 2. The antibacterial activities of 1 and 2 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli and E. cloacae have been evaluated by MTT method.     

CRYSTAL STRUCTURE OF THE METHYL 4—（N—（1—OXYPROPYL）—N—PHENYLAMINO]—1—[2—（2—THIENYL）ETHYL]—4—PIPERIDINECARBOXYLATE（R31826）HYDROCHLORIDE

<正> C22H28N2O3S.HCl, Mr = 436.9, triclinic,P1;a=8.557(3),b= 10.299(2),c= 13.894(2)A;α= 99.25(1),β=86.64(2),γ= 107.68(2)°;V= 1151.2(3)A3,Z= 2, DC = 1.27g/cm3,R=0.064. The torsion angle C(14)-C(1)-N(2)-0(19) in the title compound is 137.5 being much larger than that (106°) in R30730. The dihedral angle between mean planes of the thiophene ring and piperidine ring is about 83 .     

CRYSTAL AND MOLECULAR STRUCTURE OF N-CYANOMETHYI,BENZOIC SULFIMIDE

<正> C9HsN2O3S, Mr=222.218,monoclinic space group P21/n,B=12,584 (4).b =10.788(3), c= 15.124(4)A,β=106.83(2)°,V=1965.3A3,Dc= 0,75 g/cm3,Z=8,μ(MoKα)=1.5cm-1, F(OOO)=456(e),λ=0.7107A,R=0.067, Rw=0.059. Two Bolecules are in an asymmetric unit in the crystal. Structural analysis showed that all atoms of the two rings of benzoic sulfinide are in the sane plane which is normal to plane S(1)O(1)O(2). The C=N group is above the plane of the two rings.     

Synthesis,structure and electrochemistry of dithiocarbamato phenthiolate oxo-molybdenum(Ⅳ)complexes[MoO(SΦ)_2(S_2CNEt_2)]

The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]~- with phenthiolate [Et_4N]SΦin acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com-plex [MoO(SΦ)_2(S_2CNEt_2)]~-,which crystallizes in two forms of crystals,[Et_4N][MoO(SΦ)_2(S_2CNEt_2)](1a) and [Et_4N][MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo-noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V=2989~3,Z=4,D_c=1.35 g/cm~3 and R=0.031 for 2434 reflections [I>3(I)].1b crystallizes inthe monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27(2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm~3 and R=0.051 for 2852 independeut reflections [I>3σ(I)],The structures of 1a and 1b reveal that the anion [MoO(SΦ)_2(S_2CNEt_2)]~- contains asingle oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atomis a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linkedto oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance(1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 wasdiscussed also.     

Crystal Structure of [Et_4N][Sm(S_2CNEt_2)_4]

The crystal structure of .[Et4N][Sm(S2CNEt2)4] was determined by X-ray diffraction technique. The crystal crystallizes in monoclinic system, space group P21/n with a= 1. 1695(3), b=2.0821(6), c=1.7420(7) nm, β=99. 79(3)°? Z=4, Dc= 1. 39 g/ cm3, μ(Mo/KTσ) = 18. 4 cm-1, F(000) = 1812. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R of 0. 053 for 3116 (Ⅰ> 3σ- (Ⅰ)) reflections. Each asymmetric unit contains two ions [Sm (S2CNEt2)4]-1 and [Et4N] +1, having distance between central atoms N5 and Sm3+ to be 0. 6522 nm. The atom Sm is coordinated by eight sulphur atoms. The Sm-S distance lies in the range of 0. 285-0. 290 nm with an average of 0. 288 nm.     

Lipase immobilized on HOOC-MCF： A highly enantioselective catalyst for transesterification resolution of （R,S）-1-phenylethanol

Pseudomonas cepacia lipase (PSL) immobilized on the carboxyl-functionalized meso-cellular foams (HOOC-MCF) was used for the transesterification resolution of (R,S)-1-phenylethanol in organic solvent.The results showed that the ee value of (S)-1- phenylethanol and (R)-1-phenylethyl acetate reached 99% with 50% conversion of 1-phenylethanol using toluene as solvent. Furthermore,it was found that PSL/HOOC-MCF exhibited high enantioselectivity in organic solvent with log P≤2 such as toluene and hexane.     

Crystal Structure of Isoquinoline Derivatives

The chiral compound 5H-imidazol[2,3-b]isoquinoline-1-ethanol-5-one-1,2, 3, 10b-tetrahydro- β(S)-phenyl-3(S)-phenyl was synthesized from the direct condensation of 2-cyanophenyacetonitrile with optically active (S)-(+)-2-phenylglycinol in chlorobenzene under dry, anaerobic conditions. ZnCl2 was used as a Lewis acid catalyst in this reaction, and the structure of this compound was determined by X-ray diffraction, NMR, MS and IR. Crystal data of the title compound: C25H22N2O2, Mr = 382.45, P 21 21 21, a = 5.341(5), b = 16.735(5), c = 22.129(5) , γ = 90o, V = 1978(2) 3, Z = 4, Dc = 1.284 g/cm3, the final R = 0.0321 for 2269 observed reflections with I > 2σ(I) and Rw = 0.0771 for all data.     

Synthesis and Crystal Structure of Bis（（2-methoxy-mercaptomethyl-benzene）hexacarbonyldiiron） Complex

The reaction of [Fe2S2(CO)6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [(μ4-S){(μ-SCH2(o-OCH3)Ph)Fe2(CO)6}2](1).Complex 1 crystallizes in monoclinic,space group P21/n with a = 16.5623(6),b = 12.8265(5),c = 18.2702(7) ,β = 115.95(1)o,V = 3489.9(4) 3,Z = 4,μ = 1.87 mm-1,Dc = 1.709 Mg/m3,T = 296(2) K,C28H18Fe4O14S3,Mr = 898.03,F(000) = 1800,S = 1.10,R = 0.032 and wR = 0.058.Complex 1 consists of two diiron fragments possessing a {Fe2(CO)6} core.The two diiron units are bridged by an inorganic sulfide in a μ4-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral.In its solid state,two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.     

Syntheses, properties and structures of copper and nickel complexes of 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate

The reaction of CuCl2-2H2O or NiCl2.6H2O with K2(C5H6S4) [potassium salt of 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate] under nitrogen atmosphere resulted in the isolation of [Cu(C5H6S4)2]- or [Ni(C5H6S4)2]- as the tetrabutylammonium salt. Both complexes show characteristic IR and UV-Vis absorptions of transition metal dithiolenes. Cyclic voltammograms contain two waves indicating a two step electrochemical procedure [M(C5H6S4)2]0 = [M(C5H6S4)2]1-= [M(C5H6S4)2]2-. Single crystal structure study has been carried out on the nickel complex. Crystal of [Bu4N][Ni(C5H6S4)2] belongs to monoclinic space group P21/c with a=17.576(5), 6=10.883(2), c=17.773(4) A,B=91.07(2)0, Z=4, and o(calcd.)=1.348 g/cm3. Final result is R=0.059 for 2959 reflections. The NiS4 core exhibits square planar coordination with average Ni-S bond length of 2.134(5) A. There are not anion pairs in crystal. The anions stack along a and c axes while the cations intercalate in them. The nearest S-S contact is 4.429 A. The solid powder ESR s     

APPLICATION OF DITHIO - MOLYBDATE IN THE SYNTHESES OF Mo-Cu CLUSTERS: SYNTHESES AND CRYSTAL STRUC-TURES OF MoOS_3(CuPPh_3)(Cu(PPh_3)_2 AND (Ph_4P)_2[Mo_2Cu_5S_6O_2-(S_2CNEt_2)_3] ·DMF

<正> The reactions of (NH4)2MoO2S2 with Cu(PPh3)3Cl in CH3CN in the air, or with CuCl, Ph4PBr, and NaS2CNEt2 in DMF under anaerobic condition, afforded the cluster complexes MoS3OCu2 (PPh3)3 (Ⅰ) and (Ph4P)2 CMo2Cu5S6O2-(S2CNEt2)33 · DMF (Ⅱ), respectively. Compound (Ⅰ), MoOS3Cu2P3C54H45(Mr = 1121. 0) , crystallizes in the triclinic, space group P1 with cell parameters a = 14. 103 (3), b = 17.906(3), c=11.503(2)(?), α=107. 76(1), β=111.81(2), γ = 74.93 (2)°, F = 2532. 9(?)3 and Z=2, Dc=1. 471 g/cm3, F (000) = 1140, μ(MoKα) = 13. 215 cm-1, final R = 0. 060 (Rw = 0.064) for 5959 independent reflections with I >3σ(Ⅰ). Complex (IⅡ), Mo2O3S12Cu5P2N4C66H77 (Mr = 1930. 67) , crystallizes in monoclinic, space group P2/c with cell parameters a = 25. 325(19) , 6 = 22. 506(9) , c =14. 066(8)(?) , β =100. 96(6)°, V =7871. 16 (?)3, Z = 4, D,= 1. 629 g/cm3, F(000) = 3904, μ(MoKα) = 20. 216 cm-1, R = 0. 097 (Rw = 0. 095) for 5677 reflections with I>3σ(Ⅰ). The core structure of complex (Ⅰ) is defective cub     

Analysis of Intra-and Intermolecular Hydrogen Bonds and Quantum Chemical Calculations on 1-(3-Fluorobenzoyl)-3-(4-trifluoromethylphenyl) thiourea

1-(3-Fluorobenzoyl)-3-(4-trifluoromethylphenyl)thiourea, C_(15)H_(10)F_4N_2OS, has been synthesized firstly and determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system, space group C2/c with a = 31.87(3), b = 7.705(9), c = 12.591(14) ?, b = 106.06(2)°, V = 2971(6) ?~3, Z = 8, D_c=1.530 g·cm~(–1), F(000) = 1392, m = 0.266 mm~(–1), S = 1.06, the final R = 0.070 and w R(I 2s(I)) = 0.249. The crystal structure revealed that the carbonyl thiourea unit in the determined compound was mostly planar due in part to the formation of intramolecular N–H···O=C and C–H···S=C hydrogen bonds that form two S(6) rings. The intermolecular contacts of the crystal structure have been preformed based on the Hirshfeld surface and their associated 2D fingerprint plots. In the packing diagram of the synthesized compound, the C=S group formed two types of intermolecular hydrogen bonds by the H–N(C=O) group and the H–C of the phenyl ring, respectively, and they formed R2 2(8) and R_2~2(14) ring motifs, respectively. The crystal packing form was also stabilized by the intermolecular hydrogen bonds C–H···O(1–x, y, 0.5–z) with the R_2~2(10) ring motifs. In addition, supramolecular layers sustained by π-π stacking interactions(between the C(2)~C(7) rings with the C(10)~C(15) rings) are formed in the crystal structure of the title compound. The electronic and reactivity were assessed by the natural bond orbital(NBO) analysis in this study.     

Ethylene polymerization with novel phenoxy-imine catalysts bearing 4-vinylphenyl group

This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis(phenoxyimine) ligands. Six phenoxy-imine Ti(IV) complexes {6-R1-2-[CH=N(2,6-difluoro-3,5-diR2-4-R3Ph)]C6H3O}2TiCl2(1: R1 = H, R2 = H, R3 = H; 2: R1 = H, R2 = H, R3 = 4-vinylphenyl; 3: R1 = CH3, R2 = H, R3 = H; 4: R1 = CH3, R2 = H, R3 = 4-vinylphenyl; 5: R1 = CH3, R2 = F, R3 = H; 6: R1 = CH3, R2 = F, R3 = 4-vinylphenyl) have been synthesized and evaluated for ethylene polymerization using dried MAO(simplified as DMAO) as cocatalyst. An obvious catalytic heterogeneity of Cat 2(Complex 2/DMAO) towards ethylene polymerization was observed, which was illustrated by decreased activity, multimodal molecular weight distribution and partially improved particle morphology comparing with Cat 1. Moreover, Cat 3 exhibits "living" characteristics in the process under certain conditions(25 °C, less than 20 min). Otherwise, the moderate to high ethylene polymerization activity of ca. 105-106 g PE/(mol Ti·h) and high molecular weight(Mw = 105-106) of polyethylene can be obtained by changing the skeleton structure of these complexes.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

Synthesis and Structure of Mixed Distannoxane Dimers [ClR_2SnOSnR''''_2Cl]_2

1,1,3,3-Tetraorganodistannoxanes [XR2SnOSnR2X]2 (R = alkyl, Ph; X = halogen, NCS, OAc, OR) are a kind of organotin oxo clusters. They have received considerable attention because they are useful catalysts for many reactions1-5. And recently S. W. Ng reported that [XR2SnOSnR2X]2 (R = Bu, X = OOCCH2SC(O)N(CH2CH2)2O) had more active antitumor activity than cis-platin in vitro6. A characteristic feature of symmetric tetraorganodistannoxanes in the solid state is their dimeriz…     

Studies on Nucleophilic Ring-Opning Reaction of Ethylene Epoxide by (μ - CH,S )(μ-IMIgS ) Fea (CO)a——Syntheais and Crystal Structure of (μ-Methylthio)- (μ- R -Hydroxylethylthio)hexacarbonyldiiron

A new type of Fe-S complex (C), (μ -CH3S) (μ-HOCH2CH2S) Fe2(CO)6which contains μ-β-hydroxyethyl, has been synthesized in high yield through ring-opening reaction of ethylene epoxide under uncleophilic attack of active complex (A), (μ-CH3S)(μ-IMgS) Fe2(CO)6, followed byan alcoholysis of the intermediate (B). The crystal structure of (C)was determined by an X-ray diffraction technique. The crystal belongs to monoclinic system with space group of C2/c. Cell parameters a= 15.784(3), b = 22.172(3), c=9.774(2)A, β=119.53(2)°, V=2976.3A. Dc = 1.SOg cm-3 , Z=8, F(000)=1616 and final R=0.077.