A Novel Fused Phosphorus Heterocycle：4—（1′，2′,3′,4′—Tetrahydro—1,3,2—benzodiaaphosphorin—2′—sulfide）—3,4b,4a—thiazphosphaphenanthridine Derivative

The first example of fused phosphorus heterocyclic 4-[1′-(β-bromoethyl)-4′-oxo-3′-propyl-1′,2′,3′,4′-tetrahydro-1,3,2-benzodiazaphosphorin-2′-sulfide]-1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-3,4b,4a-thiazphosphaphenanthridine 4a,2′-dioxide was synthesized in excellent yield by refluxing a mixture of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphos phorin-4(1H)-one 2-oxide with carbon disulfide in benzene in the presence of triethylamine.     

Dehydrodimers of arylaldoxime——a convenient source of iminoxy radicals

Arylaldoxime dehydrodimers 3a—1 have been prepared from the corresponding oximes 1a—1by using (HCrO_4)_2(Py)_4Co as oxidant.Their structures were assigned to be bisnitrone by XPS studies.ESR studies of 3a—1 in hot chloroform show that iminoxy radicals 2a—1 are formed.Therefore thedehydrodimers can provide a convenient source of these radicals.     

Triply-bridged Dicopper(Ⅰ)Complex of Bis(diphenylphosphino)acetylene with a Helical Coordination Cage

<正>Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (I) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the CuACu separation of 6.231 A. The copper (I) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P 1 with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3) A, α = 98.289(1), β = 91.232(1), γ = 106.496(1)°, V = 4117.60(9) A3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr= 1659.37, Dc= 1.338 g/cm3, F(000) = 1708, μ = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I>2σ(I).     

Simultaneous assembly of mononuclear and dinuclear dysprosium(Ⅲ) complexes behaving as single-molecule magnets in a one-pot hydrothermal synthesis

Two dysprosium(Ⅲ) complexes derived from 2,2'-bipyridine-6,6'-dicarboxylic acid(H_2bpdc),[Dy(bpdc)(Hbpdc)]-3H_2O(1) and[Dy_2(bpdc)_3(H_2O)_3]·2.125H_2O(2),were isolated from the same hydrothermal reaction container as different phases.Compound1 is a mononuclear complex with a DyN_4O_4 coordination polyhedron;whereas compound 2 is a dinuclear complex with two types of eight coordinated dy sprosium(Ⅲ) ions,showing DyN_4O_4 and DyN_2O_6 coordination polyhedra,respectively.Remarkably,a new type of(H_2O)_6 supramolecular aggregate exists in the crystal structure of 2.Magnetic investigations revealed that 1 is a field-induced single-ion magnet with an effective energy barrier of 45.6 K,exhibiting two-step magnetic relaxation;while an intramolecular ferromagnetic interaction exists in 2,which is a field-induced single-molecule magnet,displaying two-step magnetic relaxation too,with effective energy barriers of 53.4 and 92.1 K,respectively.     

Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

The effects of temperature and pressure on the steam reforming of methane 3H2+CO) were investigated in a membrane reactor (MR) with a hydrogen permeable membrane. The studies used a novel silica-based membrane prepared by using the chemical vapor deposition (CVD) technique with a permeance for H2 of 6.0×l0-8 mol·m-2·s-1·Pa-1 at 923 K. The results in a packed-bed reactor (PBR) were compared to those of the membrane reactor at various temperatures (773-923 K) and pressures (1-20 atm, 101.3-2026.5 kPa) using a commercial Ni/MgAl2O4 catalyst. The conversion of methane was improved significantly in the MR by the countercurrent removal of hydrogen at all temperatures and allowed product yields higher than the equilibrium to be obtained. Pressure had a positive effect on the hydrogen yield because of the increase in driving force for the permeance of hydrogen. The yield of hydrogen increased with pressure and reached a value of 73×10-6 mol·g-1·s-1 at 2026.5 kPa and 923 K which was higher by 108% than the value of 35×10-6 mol·g-1·s-1 obtained for the equilibrium yield. The results obtained with the silica-based membrane were similar to those obtained with various other membranes as reported in the literature.     

Synthesis and Structure of a Mn（II）-triazolyl Coordination Polymer Consisting of Dinuclear Units

The reaction of bis(1,2,4-triazolyl-4-yl) (btr) and MnClO4·6H2O gave rise to a Mn(Ⅱ) complex comprised of unprecedented dinuclear Mn(Ⅱ) units, {[Mn2(btr)3(H2O)5]-(ClO4)4(H2O)2]n(1). Single-crystal X-ray diffraction analysis revealed that 1 crystallizes in the monoclinic space group C2/c. btr adopts two types of bridging modes. One serves as a μ-N1:N2 bridge through one triazolyl ring of btr forming a dinuclear Mn(Ⅱ) unit, and the other adopts an exo-bidentate mode using two nitrogen atoms from each triazolyl ring and links the dinuclear units into a 2D cationic layer. ClO4- acts as a counter anion and does not take part in coordination. Interestingly, 2D layers are packed in an ABCABC mode. ClO4- and uncoordinated water molecules locate between the adjacent layers, and extensive hydrogen bonds further stabilize the whole framework.     

Hydrothermal Synthesis and Crystal Structure of a Novel Selenite-chloride：[Cd4（SeO3）2Cl4（H2O）]n with a Three-dimensional Framework

A novel three-dimensional(3-D) compound [Cd4(SeO3)2Cl4(H2O)]n(1) was prepared from a hydrothermal reaction and structurally characterized.Compound 1 crystallizes in the space group Fmmm of the orthorhombic system with eight formula units in a cell:a = 15.5165(4),b = 17.5090(9),c = 7.3318(5) ,V = 1991.9(2) 3,Cd4Cl4H2O7Se2,Mr = 863.38,Dc = 5.758 g/cm3,S = 1.075,μ(MoKα) = 16.820 mm-1,F(000) = 3088,R = 0.0427 and wR = 0.1220.Compound 1 features a 3-D structure with the cadmium atoms having two different coordination environments,i.e.,six-and eight-coordination geometries.Two different chain-like structures of cadmium-oxo polyhedra are interconnect to each other to give a 2-D layer of [Cd4(SeO3)2(H2O)]n4n+.Between the [Cd4(SeO3)2(H2O)]n4n+ layers is a novel chloride layer.A 3-D framework is constructed from these [Cd4(SeO3)2(H2O)]n4n+ layers linked by the chloride layers.     

Synthesis and Structure of a Novel Cobalt(Ⅱ)Complex with the Tertiary Carbinol Derivative of Di-4-pyridinylmethanone

The title complex [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞ was obtained and characterized through elemental analysis, FT-IR and X-ray crystallography. The complex crystallizes in space group P3(2)21 with a=10.2480(11), b=10.2480(11), c=26.943(6), β=120.00°, [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞, C28H34CoN8O8 , Mr=669.56, Z=3, V=2450.5(7)3 , Dc=1.361 g·cm-3 , μ=0.584 mm-1 , F(000)=1047, R=0.0498 and wR=0.1301. The Co(Ⅱ) center exhibits a N4O2-octahedral coordination geometry surrounded by a pair of nitrates at the axial positions and four pyridyl N atoms at the equatorial sites. An infinite double-bridged chain structure with μ2-bridging (4-C5H4N)2C(OH)(NHC3H7) ligands is formed, which is the in situ product of metal-promoted nucleophilic addition reaction of propan-1-amine with di-4-pyridinylmethanone ((4-C5H4N)2CO) in the presence of Co(NO3)2·6H2O. It is the first tertiary carbinol metal complex derived from di-4-pyridinylmethanone so far, and also the rare example of tertiary carbinol derivative of dipyridylmethanone family. The nucleophilic reaction at the carbonyl of dipyridylmethanone in the presence of metal salt will be discussed.     

Synthesis, Crystal Structure and Photoluminescence of a 2D Two-fold Interpenetrating Cd(Ⅱ) Coordination Polymer Based on a Flexible Reduced Schiff Base Ligand

<正>By the reaction of cadmium chloride with a reduced Schiff base ligand (H_2L = N-(4- carboxybenzyl)-glycine), a novel Cd(II) compound [Cd(HL)_2]·4H_2O (1) has been obtained. Single-crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic, space group Pbcn with a = 13.9788(8), b = 24.4204(14), c = 13.9580(8), V = 4764.8(5)~3, Z = 8, M_r = 600.84, D_c = 1.675 g/cm~3, μ = 0.983 mm~(-1), F(000) = 2448, S = 1.084, R = 0.0806 and wR = 0.1705 (I > 2σ(I)). It displays a 2D two-fold interpenetrating structure. The Cd(II) ions are six-coordinated. The cross-linkage of Cd(II) ions by the bridge of HL anions results in a [Cd(HL)_2] layer. Every two [Cd(HL)_2]_n layers are penetrated with each other, resulting in a two-fold interpenetrating double-layer structure by π-π stacking interactions and hydrogen bonds. Such double-layers are further linked by hydrogen bonds into a supramolecular structure. Photoluminescent investigation shows that compound 1 displays strong emission in the purple region.     

A Novel Fused Phosphorus Heterocycle: 4-(1′, 2′, 3′, 4′-Tetrahydro- 1, 3, 2-benzodiazaphosphorin-2′-sulfide)-3, 4b, 4a- thiazphosphaphenanthridine Derivative

The first example of fused phosphorus heterocyclic 4-[ l′-(β-bromoethyl)-4'-oxo-3'-prop yl-1′, 2′, 3′, 4-tetrahydro-1, 3, 2-benzodiazaphosphorin-2′-sulfide]-1, 2, 3, 4, 4a, 4b, 5, 6-octahydro -6-oxo-5-propyl-3, 4b, 4a-thiazphosphaphenanthridine 4a, 2′-dioxide was synthesized in excellent yield by refluxing a mixture of 1-(2-bromoethyt)-2, 3-dihydro-3-propyl-l, 3, 2-benzodiazaphos phorin-4(1H)-one 2-oxide with carbon disulfide in benzene in the presence of triethylamine.     

Activation of Nitromethane to Cyanide by a Mononuclear Cu(Ⅱ) Complex

The tridentate ligand DPA-Me(2) was readily prepared from DPA(DPA = 2,2-dipicolylamine) in high yield. The mixture of 2 and Cu(Cl O4)26H2O in methanol gave a five-coordinated mononuclear complex [(DPA-Me)Cu(Me CN)(Cl O4)](Cl O4)(3). Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu(DPA-Me)]2(CN)(Cl O4)3CH3NO2}n(4). Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a = 17.74582(15), b = 13.89877(11), c = 14.92546(13) , β = 91.4246(8)°, V = 3680.15(5) 3, Z = 4, Dc = 1.695 g/cm3, F(000) = 1912, C28H33Cl3Cu2N8O14, Mr = 939.05, μ = 1.602 cm-1, Cu Kα radiation(λ = 1.54184 ), R = 0.0485 and w R = 0.1246 for 6414 observed reflections with I 2σ(I).     

Synthesis and Characterization of a Novel Compound SnDy2O4

In recent years, the research on rare earth became a focus, and a lot of rare earth complex compounds with AB2O4 stoichiometry were prepared1-3. The compound SnDy2O4 is expected to spinel-type phase while it exhibits a new structure type. SnDy2O4 was prepared by the thermal decomposition of the oxalate precursor that was prepared by rheological phase reaction method. SnO(AR), Dy2O3(99.9%) and H2C2O4·2H2O are ground in molar ratio 1:1:4.1, and placed into the reaction apparatus. …     

Synthesis, molecular structure and intramolecular aromatic-ring stacking interaction of a novel binuclear Cu(Ⅱ) complex with 1, 10-phenanthroline and phenylacetate

The complex [Cu(phen)2(POAc)3]ClO·4H2O has been synthesized and investigated by elemental analysis, IR spec-troscopy and X-ray diffraction methods, where phen = 1,10-phenanthroline, POAc = phenylacetate group). The complex crystallizes in the triclinic space group PI with two molecules in a unit cell of dimensions a = 1.0579(2) nm, b = 1.2423(3) nm, c = 1.9190(4) nm, α = 71.84(1)°, β = 80.50(2)°, γ = 88.60(1)°, V = 2.3625(9) nm3, R = 0.0407 and Rw = 0.0656. The complex results from bridging of two Cu(phen)2 units by three carboxylate groups, and each Cu2 ion is in a distorted square pyramidal geometry with two nitrogen atoms of phen and three carboxylate oxygen atoms of POAc. It has been showed that intramolecular stacking interactions occur between the phenyl moieties of POAc and aromatic rings of phen, leading to a novel molecule structure with two coordinating modes of carboxylate ligands, of which two phenylacetates are μ2-carboxylate-O-bridging ligands, and the other is a μ2-carboxylate-     

Synthesis and Crystal Structure of a Binuclear Cobalt（ Ⅱ） Carboxyla

Reaction of cobalt carbonate, pivalic acid and quinoline in a refluxing ethanol solvent yielded the dicobalt(Ⅱ) compound, Co2(O2CCMe3)4(C9H7N)2 (1) (C9H7N is quinoline), which has been characterised by elemental analysis, IR and X-ray diffraction method. Crystallographic data: monoclinic, P21/a, a=9.341(2), b=18.591(4), c=11.822(2)(), β=97.71(2), V=2034(1)()3, Z=2, Mr=918.19, Dc=1.27 g/cm-3, F(000)=820, μ(MoKα)=8.60 cm-1, T=293K, final R=0.049, Rw=0.060 for 2715 observed reflections with I>3.0 σ(I). The centrosymmetric molecule comprises a pair of cobalt(Ⅱ) atoms connected by four pivalate ligands in syn-syn bridging modes. Square pyramidal five-coordination of cobalt(Ⅱ) is further completed by a quimoline molecule. The CoⅡ-CoⅡ distance is 2.784(1)().     

Construction of a Set of Cadmium（Ⅱ） Coordination Polymers with Atza and 2,2′-Bipy or 1,10-Phen Ligands （Atza=5-Aminotetrazole-1-acetato Anion）

Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd(Ⅱ) coordination polymers, {[Cd(atza)(H2O)(2,2′-bipy)]ClO4}n (1), {[Cd(atza)(H2O)(1,10-phen)]ClO4 }n (2), {[Cd(atza)(H2O)(2,2′-bipy)]NO3}n (3) and {[Cd(atza)2 (1,10-phen)]·0.5H2O}n (4). Single-crystal X-ray diffraction analysis reveals that each Cd(Ⅱ) ion has a distorted octahedral coordination geometry in 1-4, and the Cd(Ⅱ) ion centers are connected through the tridentate atza bridging ligands to form a 2D layer (1-3) or ID chain (4) structure. The fluorescent properties of 2 and 4 are also discussed.     

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.     

Solvothermal Synthesis and Crystal Structure of a Layered Thioantimonate(Ⅲ) [C_4H_9NH_3]_2Sb_4S_7

An inorganic-organic hybrid thioantimonate(Ⅲ) [CH3(CH2)3NH3]2Sb4S7 1 with layered structure was synthesized by solvothermal method. 1 crystallizes in the triclinic system,space group P1 with a=7.0124(11),b=11.919(2),c=14.879(3),α=108.791(3),β=102.441(3),γ=92.846(2)o,V=1140.1(3)3,Mr=859.71,Z=2,Dc=2.504 g/cm3,μ =5.324 mm-1,F(000)=804,S=1.013,the final R=0.0297 and wR=0.0618 for 3534 observed reflections with I > 2σ(I). 1 consists of [C4H9NH3]+ cations and two-dimensional [Sb4S7]n2n- anion which is composed of three SbS3 trigonal pyramids and one SbS4 unit joined by sharing common corners. The anionic layers are stacked perpendicularly to the c axis of the unit cell forming two-dimensional channels between the layers. The [C4H9NH3]+ cations interdigitate in a bilayer and reside in the 2D channels leading to a sandwich-like arrangement of the anion and cations.     

A NEW CONVENIENT METHOD FOR THE SYNTHESIS OF PERFLUOROALKYL 2H-PYRROLE

The reaction between 2,5-Dimethylpyrrole (1) and R_FI (2)(R_F: a, Cl(CF_2)_4; b, Cl(CF_2)_6; c, Cl(CF_2)_8; d, n-C_6F_(13); e, n-C_8F_(17)) in the presence of Na_2S_2O_4-NaHCO_3 in acetonitrile resulted in the formation of 2-perfluoroalkyl-2,5-dimethyl-2H-pyrrole (3) as a major product in good yield.     

Synthesis and Characterization of Ti-ZSM-5 in a Non-alkaline Medium in the Presence of Fluoride Ions

Ti-ZSM-5 was synthesized by hydro thermal crystallization in the presence of fluoride via using a non-alkaline medium. pH values were 5~7. SEM showed perfect Ti-ZSM-5 crystals and a large single crystal growing from the favourable medium. Substitution of titanium for silicon in the ZSM-5 framework led to a decrease of crystal size and of the length/width ratio. Electron microprobe analysis indicated a homogeneous distribution of titanium in the ZSM-5 framework. The unit cell parameters of the Ti-ZSM-5 determined by XRD increased with an increase in titanium content in the framework. TiO4tetrahedron vibrations were found in the IR spectrum. Si(1Ti) peakwas seen in the 29Si MAS NMR spectrum at -1O1ppm(from TMS) and 13CMAS NMR analysis verified the effect of (C3H7)4N F- occluded in thechannels. XPS study on the precursors, calcined and H2O2 adsorbed Ti-ZSM-5 was performed and some interesting results were observed.     

SYNTHESIS AND OPTICAL PROPERTIES OF POLY (THIENYLACETYLENES)*

3 -Ethynyl-4-(trimethylsilyl)thiophene (1a) and 3 -ethynyl-4-bromothiophene (1 b ) selectivelyundergo acetylene polymerizations in the presence of the MoCl_5- and WCl_6-Ph_3SiH catalysts to give soluble,high-molecular-weight poly(thienylacetylenes) (2) (M_w up to 602000) in high yields (up to 100%). Lighttransmission spectra of THF solutions of 2 continuously red-shift with increasing concentration. Theconcentratochromism shows a logarithmic concentration dependence; that is, the optical transitions of 2 arepredictably tunable by simply changing their concentrations.