Coordination Triangular Prism of Bisilver Complex with Triply-bridged of Bis(diphenylphosphino)amine

The binuclear complex [Ag2(m-Ph2PNHPPh2)3](ClO4)2CH2Cl2CH3OH (Ph2PNHP- Ph2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis- (diphenylphosphino)amine in equimolar ratio through self-assembly. The coordination cation affords a triply-bridging [Ag2L3]-type coordination moiety. The silver atom is in a trigonal planar environment with P3 coordination chromophore. The complex (C74H69Cl4N3O9P6Ag2) crystallizes in monoclinic, space group Cc with a = 18.3738(1), b = 20.0207(4), c = 20.5422(4) ? b = 95.829(1), V = 7517.5(2) 3, Z = 4, Mr = 1687.68, Dc = 1.491 g/cm3, F(000) = 3432, m = 0.848 mm-1, the final R = 0.0460 and wR = 0.0935 for 7005 observed reflections with I > 2s(I).

Synthesis and Crystal Structure of a Tetranuclear Silver Complex with Bis(diphenylphosphino) amine-dioxide as a Tridentate Ligand

The tetranuclear complex[Ag4（μ-Ph2PNHPPh2）2（μ-OPh2PNPPh2O）2] （PF6）2·CH3COCH3 containing bis（diphenylphosphino）amine （Ph2PNHPPh2） and deprotonated bis- （diphenylphosphino）amine-dioxide （OPh2PNPPh2O） was isolated and characterized by X-ray crystallography. The deprotonated OPh2PNPPh2O acts as a tridentate ligand in a chelating and bridging mode. Two of the four Ag atoms are in a trigonal planar environment composed of PO2 chromophore, whereas the other two are coordinated with PN donors in a distorted linear arrangement. The title complex （C51H47Ag2F6N2O3P5） crystallizes in triclinic, space group P1^- with a = 12.9552 （2）, b = 14.1691（3）, c = 15.8110（3）A°, α = 68.7500（10）, β= 86.8840（10）, γ = 75.6170（10）°, V= 2618.16 （8） A°^3, Mr= 1220.50, Z = 2, Dc= 1.548 g/cm^3, F（000） = 1228 and μ（MoKα） = 0.965 mm^-1. The final refinements converged at R = 0.0679 and wR = 0.1528 for 7001 observed reflections （I〉 2σ（I））.

Heterotetranuclear Cu_2~IPd_2~Ⅱ Complex with Bis(diphenylphosphino)methane and Diethyldithiocarbamate

Self-assembly between the building blocks of Pd(Et2dtc)2 (Et2dtc = diethyldithio- carbamate) and [Cu2(m-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) gave a new heterotetranuclear complex [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3-Et2dtc)2](ClO4)2H2O (C70H86Cl2Cu2- N4O9P4Pd2S8, Mr = 1932.56), and its crystal structure has been determined by X-ray crystallo- graphy. It crystallizes in triclinic, space group P with a = 11.9834(6), b = 12.5624(6), c = 14.5603(8) ? a = 101.393 (1), b = 103.300 (1), g = 96.310(1), V = 2063.2(2) 3, Z = 1, Dc = 1.544 g/cm3, m(MoKa) = 1336 cm-1 and F(000) = 978. The total and unique reflections are 8710 and 5400, respectively. The structure was refined to R = 0.0860 and wR = 0.1996 for 3914 observed reflections with I > 2s(I). The title complex consists of the cation [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3- Et2dtc)2]2+, anion ClO4- and solvate H2O. The Pd(Ⅱ) atoms are located at the approximately square-planar environments with PS3 donors and the Cu(I) atoms display distorted tetrahedral geometries.

Synthesis, Characterization, and Reactivity of Amine Bis(phenolato) Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.

An Exploratory Study of Tridentate Amine Extractants: Solvent Extraction and Coordination Chemistry of Base Metals with <i>Bis</i>((1<i>R</i>-benzimidazol-2-yl)methyl)amine

Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.

Synthesis and Antimicrobial Properties of the Novel Fluonnated Bis-ammonium Salts with Two Primary Amine Groups

In order to resolve the increasing resistance phenomena of the Gram-negative bacteria against single chain quaternary ammonium salts （QAS）, lysine with a pedant fluorinated bis-ammonium salts was synthesized and its antimicrobial properties were evaluated in this work. The novel fluorinated bis-ammonium salts shows similar activity with conventional single chain quaternary ammonium salts against Gram-positive bacteria but stronger activity against Gram-negative bacteria and yeast compared with the single chained counterpart.

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

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).

Catalytic Effect of Cobalt and Iron Complexes Incorporating Bis(2-aldiminoethyl)amine Ligands on Ethylene Oligomerization

Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of each of complexes 3-5 with ethylaluminoxane(EAO), respectively, was found to be moderately active for ethylene oligomerization to low carbon olefins. The activity of 113 kg oligomers·mol -1 Co·h -1 for complex 3(100 mol of EAO, 180 ℃ and 1 8 MPa ethylene) was observed with a selectivity of 93% to C 4-10 olefins, of which 96% were linear C4 10 olefins. The catalytic properties of complexes 3-5 were compared with those of analogous P,P coordinated complexes [MCl 2{CH 3N(CH 2CH 2PPh 2) 2}](1, M=Co; 2, \{M=\}Fe).

Synthesis,Crystal Structure and Blue Photoluminescence of a Metal-organic Framework Constructed from Triangular [Zn_3(μ_3-OH)] Clusters with Bis(tetrazole)amine Ligands

A new metal-organic framework, {Zn[Zn3（BTA）3（μ3-OH）（H2O）3]2}n 1, has been synthesized under hydrothermal reaction of ZnCl2 and bis（5-tetrazolyl）amine （H2BTA）, and characterized by elemental analysis, FT-IR, Raman spectrum, X-ray single-crystal diffraction, TGA and photoluminescence measurements. Compound 1 crystallizes in the trigonal system, space group P-3cl, a = 13.667（3）, c = 12.981（3） A, V = 2099.6（8） A3 and Z = 2. The BTA2- ligand in 1 assumes theμ3 tetradentate mode with both 1,2- and 1,4-tetrazole bridges, generating an unusual 2-D layer, in which the [Zn3（μ3-OH）] triangular motifs act as three-connecting nodes and the mononuclear Zn atoms as six-connecting nodes that are inter-linked by organic ligands. Adjacent 2-D metal-organic layers are linked by strong hydrogen bonds to form a novel 3-D supramolecular framework. Complex 1 exhibits blue fluorescence emission in the solid state at ambient temperature.

Identification of N-Methyl Bis(2-(Alkyloxy-Alkylphosphoryloxy)Ethyl) Amines by LC-HRMS/MS

N-Methyl bis(2-(alkyloxy-alkylphosphoryloxy)ethyl)amines, which are abbreviated as PNPs, are a series of new skeleton chemicals belonging to schedule 2.B.04 chemicals of Chemical Weapons Convention (CWC). PNPs are important markers of chemical warfare agents because they are structurally relative to both nerve agents and N-mustards. In this study, fragmentation pathways of the most characteristic fragment ions in Q-TOF mass spectrometry were proposed based on the information from accurate mass and secondary fragmentations of product ions scan experiments. Results indicated that the base ion in LC/HRMS was the quasi-molecular ion [M+H]+. In LC-HRMS/MS, it was [M+H-CnH2n+1P(O)(OH)CmH2m+1O]+ fragment ion which was formed by losing an alkyloxy alkylphosphoryloxy group from the quasi-molecular ion. The diagnostic ion m/z84.0814 was identified as [C5H10N]+, which was the group of (CH2=CH)2N+(H)CH3. PNPs have two protonated centers. One is on the N atom, the other is on the O atom (P=O). O-n-propyl PNPs generally exhibited two fragmentation pathways. Firstly, the quasi-molecular ion [M+H]+ lost a propoxy alkylphosphoryloxy group to produce [R1P(OH+)(O-n-C3H7)OCH2CH2N(CH3)CH=CH2]+, which could be fragmented further to produce [C5H10N]+ ion. Secondly, [R1P(OH+)(O-n-C3H7) OCH=CH2]+ ions were produced from [M+H]+ and fragmented further to produce the abundant ions [R1P(OH+)(OH)OCH =CH2]. However, O-isopropyl PNPs characteristically produced weak fragment ions [M+H-C3H6]+, which were presumably formed via loss of CH3CH=CH2 from [M+H]+. Other PNPs showed similar fragmentation pathways as O-n-propyl PNPs. On the summarization of the MS fragmentation pathways of PNPs, LC-HRMS/MS quantitative and qualitative methods were developed and applied to analyze N-Methyl bis(2-(butoxy-methylphosphoryloxy)ethyl]amine in high background organic samples. The analytical results had successfully supported the sample preparation for the 33rd official proficiency test of Organization for Prohibition of Chemical Weapons (OPCW).

The Influence of Ketones on the Formation of Symmetrical Secondary Amine: A New Method for Preparation of N, N-Bis-(dimethoxyphenylethyl)amine

The influence of some ketones on the formation of symmetrical secondary amine N, N-bis-(3, 4-dimethoxyphenylethyl)amine 1 were discussed and a new method For preparing 1 was described.

Synthesis and Structure of Zinc Complex of N, N-bis ( benzimidazol-2-yl-methyl ) amine

The Zinc complex of N, N-bis (benzimidazol 2-yl-methy])amine has been synthesized and its crystal structure determined by X-ray diffraction method. The structure features of the complex are described.

Synthesis of Racemic Bis[2-(6-fluoro-2-chromanyl)-2-hydroxyethyl]-amine Methanesulfonic Acid Salt Using Lithium Aluminum Amide as a Promoter in Regioselective Ring Opening of Epoxide

Lithium aluminium amide [LiAI（NHR）4] 5 obtained by treating the primary amine 4 with LiAlH4 could promote the ring opening of epoxide 2 and led to high regioselective product of racemic bis[2-（6-fluoro-2-chromanyl）-2-hydroxyethyl]amine methanesulfonic acid salt 7.

Computational Study for the Aromatic Nucleophilic Substitution Reaction on 1-Dimethylamino-2,4-bis(trifluoroacetyl)-naphthalene with Amines

Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.

锂电池电解液功能添加剂乙二醇(双丙腈)醚的合成研究

提供了一种高效的乙二醇(双丙腈)醚的合成方法,该方法是在催化剂二-(三甲基硅基)胺基锂(20%四氢呋喃溶液)作用下,以乙二醇和丙烯腈为原料一步法反应得到。该反应条件温和,反应温度控制在35℃左右,反应结束后,先用稀硫酸调节pH值至6左右,然后减压蒸馏除去未反应的丙烯腈、四氢呋喃以及少量水分,再经过高真空精馏即可得到纯度大于99.9%的产品乙二醇(双丙腈)醚。该合成方法的物质的量收率以乙二醇计大于90%,并且中间体单醚经回收套用后,物质的量收率可达到95%,该工艺既可满足作为高品质锂离子电池电解液添加剂的应用要求,又可用于大规模的工业化生产。

Ruthenium Bisphosphine Catalyst on Functionalized Silica: Novel Efficient Catalyst for Carbon Dioxide Hydrogenation to Formic Acid

A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency （TOF） of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.

Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Synthesis of bis(amino)furans from biomass based 5-hydroxymethyl furfural

In this study we report a new reaction pathway in which the hydroxyl and the aldehyde groups of 5-hydroxymethyl furfural were aminated respectively. Hydroxyl group was aminated via Ritter reaction followed by direct reductive amination of aldehyde group. For the Ritter reaction of 5-hydroxymethyl furfural, mixture of trifluoromethane sulfonic acid and phosphoric anhydride showed good performance and the intermediate N-acyl-5-aminomethyl furfural with the highest yield of 89.1 wt% was obtained.Optimization of direct reductive amination of 2,5-bis（aminomethyl） furan was conducted and a yield of45.7 wt% was achieved. This study presents a simple way for preparing bis（amino）furans from renewable biomass based 5-hydroxymethyl furfural, which enriches the biorefinery concept from biomass.

Synthesis and Crystal Structure of Bis(μ-bis(diphenyl- phosphino)methane)(μ-benzenethiolate)(acetonitrile) Dicopper(I) Perchlorate Diethylether Solvate

The reaction between [Cu2(m-dppm)2(MeCN)4](ClO4)2(dppm = bis(diphenylphos- phino)methane) and [Zn(PhS)2(bpy)] (bpy = 2,2-bipyridine, PhS = benzenethiolate) gave the complex [Cu2(m-dppm)2(m-PhS)(MeCN)]ClO40.5(Et2O)(C58H52ClNO4P4SCu20.5Et2O) which was determined by X-ray single-crystal diffraction. The crystal is of orthorhombic, space group P212121 with a = 13.6157(3), b = 20.8022(6), c = 21.3299(6) ? V = 6041.4(3) 3, Mr = 1182.54, Dc = 1.300 g/cm3, F(000) = 2444, m = 0.934 mm-1 and Z = 4. The final R = 0.0773 and wR = 0.1843 for 7744 observed reflections (I > 2s(I)). The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate. One copper atom is in a distorted trigonal bipyramidal environ- ment, whereas the other adopts a distorted tetrahedral geometry.

Synthesis and Crystal Structure of a New Ternary Mixed Ligand Complex [Cu(ampym)(bapa)Cl](ClO_4) (ampym = 2-Aminopyrimidine, bapa = Bi(3-aminopropyl)amine)

The title complex [Cu（ampym）（bapa）Cl]（ClO4） （C10H22Cl2CuN6O4） was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The crystal crystallizes in the orthorhombic system, space group Pna21 with a = 11.9904（12）, b = 15.9796（16）, c = 8.9 i 43（9） A^°, V = 1708.0（3）A^°3 Mr = 424.78, Z = 4, F（000） = 876, Dc = 1.652 g/cm^3, T = 293 K,μ =1 .619 mm^-1 and λ=0.71073 A^°. The structure was refined to R = 0.0240 and wR ： 0.0564 for 2905 observed reflections with I 〉 2σ（I）. Flack = 0.039（12）.