(1S,3S)-1,3-二苯基-1,3-丙二胺的合成

以二氯甲烷作溶剂,N-Boc保护的二氢吡唑在六甲基磷酰胺存在下与苯基格氏试剂反应,比较大量地制备了对应的四氢吡唑(4);再由4合成消旋的1,3-二苯基-1,3-丙二胺(1,总收率35%);1经L-二苯甲酰酒石酸盐拆分制得光学纯的(1S,3S)-1,3-二苯基-1,3-丙二胺,其结构经1HNMR确证。     

β-diketone interactions: Part 4. The structures and properties of 1,3-diphenyl-2-methylpropane-1,3-dione,C16H14O2, and 1,3-diphenyl-2-(4-methoxyphenyl)propane-1,3-dione,C22H18O3

The X-ray crystal structures of 1,3-diphenyl-2-methylpropane-1,3-dione and 1,3-diphenyl-2-(4-methoxyphenyl)propane-1,3-dione show them both to adopt cis-diketo (Z,Z) conformations with carbonyl—carbonyl dihedral angles of 89.0(3)° (2-methyl derivative), and 85.5(4)° and 77.7(4)° for the two molecules in the asymmetric unit of the 2-(4-methoxyphenyl) derivative. These are the first acyclic β-diketones with an α-hydrogen to be reported which do not have an enol configuration in the solid state.     

Metal derivatives of 1,3-bis(2-pyridyl)-1,3-propanedione and N,N′-dimethyl-1,3-bis(2-pyridyl)-1,3-propanedione

Complexes of transition metal ions with the oxygen-nitrogen containing ligand 1,3-bis(2-pyridyl)-1,3-propanedione (bpypH) have been synthesized. These present stoichiometries which do not conform with the usual tendency manifested by β-diketones, since molecular formulas with the composition M(bpyp)X are found. A nitrogen methylated ligand N,N′-dimethyl-1,3-bis(2-pyridyl)-1,3-propanedione methyl sulphate [dimebpypH] (MeSO₄)₂ has also been synthesized and its complexes with transition metal ions studied. The stoichiometries now, resemble those of typical β-diketones, namely [dimepyp]₂MX₄ with four anions because of the dicationic nature of the original ligand. This, together with IR evidence suggests a dual type of coordination by bpip via the β-diketone and the pyridyl moieties.     

Synthesis and crystal structure of aquabis(isothiocyanato)(18-crown-6)lead(II)(isothiocyanato)-(18-crown-6)(nitrato-<Emphasis Type="Italic">O,O</Emphasis>′)lead(II)

A new mixed complex compound, aquabis(isothiocyanato)(18-crown-6)lead(II)(isothiocyanato)-(18-crown-6)(nitrato-O,O′)lead(II) [Pb(NCS)₂(18-crown-6)(H₂O)][Pb(NCS)(NO₃)(18-crown-6)] is prepared, and its crystal structure is studied by XRD analysis. The structure was solved by the direct method and was refined by full-matrix least-squares method in anisotropic approximation to R = 0.044 for all 3648 measured independent reflexes (automatic diffractometr CAD-4, λMoK _α). This crystal structure contains two symmetrically independent halves of the two individual and differing in type complex “guest-host” molecules. One of them (with the H₂O ligand molecule) is located on the crystallographic axis 2, and the other is located around the crystallographic inversion center and is statistically disordered relative to this center (except for its crown-ligand).     

Synthesis,crystal structure,and magnetic properties of a new end-to-end thiocyanato-bridged dicobalt(II) complex CoII(dien)(H2O)(NCS)(μ1,3-NCS)CoII(dien)(NCS)2 (dien = diethylenetriamine)

Synthesis, characterization, crystal structure, and magnetic properties of the first single µ_1,3-thiocyanato-bridged dicobalt(II) compound, [Co^II(dien)(H₂O)(NCS)(µ_1,3-NCS)Co^II(dien)(NCS)₂] (1; dien = diethylenetriamine), are described. In 1, cobalt(II) is six coordinate with distorted-octahedral geometry. The Co(1) ··· Co(2) distance is 5.99 Å. The magnetic properties of 1 have been investigated by variable-temperature magnetic susceptibility measurements. The metal centers are coupled by weak ferromagnetic interaction (J = 1.14 cm^?1). The structure and magnetic properties are compared with related thiocyanate-bridged compounds.     

Formation and isomerization of cis,cis-Ir(H)2(--Ph)(CO)(PPh3)2 and cis,cis-Ir(H)(--Ph)2(CO)(PPh3)2 in oxidative addition of hydrogen and phenylacetylene to trans-Ir(CO)(--Ph)(PPh3)2

Oxidative addition of H–R (H--Ph and H₂) to trans-Ir(--Ph)(CO)(PPh₃)₂ (2) gives the initial products, cis, cis-Ir(H)(--Ph)₂(CO)(PPh₃)₂ (3a) and cis, cis-Ir(H)₂(--Ph)(CO)(PPh₃)₂ (3b), respectively. Both cis-bis(PPh₃) complexes, 3a and 3b undergo isomerization to give the trans-bis(PPh₃) complexes, trans, trans-Ir(H)(--Ph)₂(CO)(PPh₃)₂ (4a) and cis, trans-Ir(H)₂(--Ph)(CO)(PPh₃)₂ (4b). The isomerization, 3b→4b is first order with respect to 3b with k₁=6.37×10⁻⁴ s⁻¹ at 25°C under N₂ in CDCl₃. The reaction rate (k₁) seems independent of the concentration of H₂. A large negative entropy of activation (ΔS^≠=−24.9±5.7 cal deg⁻¹ mol⁻¹) and a relatively small enthalpy of activation (ΔH^≠=14.5±3.3 kcal mol⁻¹) were obtained in the temperature range 15∼35°C for the isomerization, 3b→4b under 1 atm of H₂.     

Neodymium(III) triaquatrihydroxo(1,3-diamino-2-propanoltetraacetato)germanium(IV) hydrate [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>] · H<Subscript>2</Subscript>O: Synthesis and crystal and molecular structure

The heteronuclear germanium(IV) and neodymium(III) complex with 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H₂O)₃] · H₂O has been synthesized for the first time and characterized by physicochemical methods (elemental analysis, X-ray powder diffraction, thermogravimetry, IR spectroscopy, X-ray crystallography). The crystals are monoclinic: a = 9.331(3) Å, b= 10.279(4) Å, c = 21.474(7) Å, β = 94.59(3)°, V = 2053.0(12) ų, Z = 4, space group P2₁/n, R1 = 0.0245 for 4060 reflections with I > 2σ(I). The compound is built of complex binuclear molecules [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H₂O)₃] and water molecules of crystallization. The germanium and neodymium atoms are bridged by the oxygen atom of the hydroxo group (Ge-O, 1.798(2) Å; Nd-O, 2.539(2) Å) and the deprotonated oxygen atom of the isopropanol group of the HHpdta^4? ligand (Fe-O, 1.858(2)Å; Nd-O, 2.420(2) Å) to form a dimeric molecule. Each coordination sphere (of the Ge atom and of the Nd atom) contains one nitrogen atom (Ge-N, 2.096(3) Å; Nd-N, 2.807(2) Å) and two carboxylic oxygen atoms from four acetate branches of the octadentate HHpdta^4? ligand (av. Ge-O, 1.928(2) Å; Nd-O, 2.391(2) Å). The coordination polyhedron of the Ge atom is completed to a distorted octahedron by the oxygen atom of the terminal hydroxo group (Ge-O 1.811(2) Å), and the polyhedron of the Nd atom is completed to a nine-vertex polyhedron by the oxygen atoms of the terminal hydroxo group (Nd-O 2.494(3) Å) and three water molecules (Nd-O, 2.512(3), 2.520(3), and 2.723(3) Å). In the crystal structure, the complex molecules and the water molecules of crystallization are joined by a hydrogen bond system.     

α,β-(Phosphino)(aminocarbene) and α,ω-(phosphino)(oxyaminocarbene): new bidentate ligands for transition metal complexes

Direct complexation of (amino)(phosphino)carbene 1a and (amino)(oxy)carbene 1b featuring a phosphino group in position-6 to the carbene with [Rh(CO)₂Cl]₂ has been studied. With the 1,2-bidentate ligand 1a, an original cationic complex 2 featuring two (amino)(phosphino)carbenes η²-bonded to the metal has been isolated in 79% yield. In the case of the 1,6-bidentate ligand 1b, a rhodium(I) complex 3 in which the carbene is in trans position relative to the CO ligand was obtained in 85% yield. Both compounds were fully characterized including X-ray diffraction studies.     

Cluster synthesis 37—Platinum-ruthenium carbido-cluster complexes: The syntheses and structural characterizations of PtRu5(C)(CO)16, Pt2Ru5(C)(CO)13(COD)2, and Pt3Ru5(C)(CO)14(COD)2

From the reaction of [Ru₅(C)(CO)₁₄]^2– with Pt(COD)Cl₂, COD=1, 5 cyclooctadiene, the new platinum-ruthenium carbido cluster complex PtRu₅ (C)(CO)₁₄(COD),1, was obtained in 41% yield. When1 was allowed to react with carbon monoxide (25°C/1 atm), the new complex PtRu₅(C)(CO)₁₆,2, was obtained almost quantitatively (97% yield). Compound2 was characterized by IR and single-crystal X-ray diffraction analysis. The six metal atoms are arranged in the form of an octahedron with the carbide ligand located in the center. Compound1 is believed to have a similar structure to2 except for a COD ligand coordinated to the platinum atom. When activated by treatment with Me₃NO, compound2 reacts with Pt(COD)₂ at 25°C to yield two higher nuclearity cluster complexes, Pt₂Ru₅C(CO)₁₃(COD)₂.3, and Pt₃Ru₅C(CO)₁₄(COD)₂,4. The structure of3 is similar to that of1, but contains a Pt(COD) grouping capping one Ru₃ triangle of the PtRu₅ octahedron. The structure of4 consists of a PtRu₅ octahedron with two Pt(COD) capping groups, one on an Ru₃ triangle and the other on a PtRu₂ triangle of the octahedron. Crystal data: for2, space group=P2₁/n,a=9.341 (2) Å,b=14.957 (3) Å,c=36.80 (1) Å, =90.38 (2) °,Z=8, 4034 reflections,R=0.030, for3, space group=P2₁/c,a=14.998 (3) Å,b=10.288 (3) Å,c=26.581 (7) Å, =102.75 (2) °,Z=4, 2917 reflections,R=0.028. for4, space group=P2₁/n,a=13.412 (4) Å,b=16.252 (4) Å,c=20.107 (4) Å, =106.13 (2) °,Z=4, 2745 reflections,R=0.032.     

二维M_2XO_(2-2x)(OH)_(2x)(M=Ti,V;X=C,N)析氢催化活性的第一性原理研究

MXene是一种新型的二维析氢催化材料,其表面容易被亲水基团O和OH混合覆盖。我们基于第一性原理计算的方法,研究了M_2XO_(2-2x)(OH)_(2x)(M=Ti,V;X=C,N)的析氢催化活性。计算结果显示,M_2XO_(2-2x)(OH)_(2x)的析氢催化活性与其表面OH覆盖率(X)密切相关。对Ti_2CO_(2-2x)(OH)_(2x)来说,OH覆盖率不超过1/3时,具有优异的析氢催化活性。对Ti_2NO_(2-2x)(OH)_(2x)、V_2CO_(2-2x)(OH)_(2x)和V_2NO_(2-2x)(OH)_(2x)来说,OH覆盖率分别达到4/9、1/3和5/9时,才具有最佳的析氢催化活性。接着,电荷分析显示OH覆盖率会显著影响M_2XO_(2-2x)(OH)_(2x)活性位点O基团的电荷量。最后,我们从态密度的角度揭示了析氢催化活性变化的原因,即活性位点O基团的氧化性随OH覆盖率的增大而被削弱。因此,本文提出了调节表面OH覆盖率来获取M_2XO_(2-2x)(OH)_(2x)最佳析氢催化活性状态的方法,这在工业制氢生产过程中具有重要的应用价值。     

1,3-二氯-1,1′,3,3′-四(1,3-二苯基-1,3-丙二酮)-μ-氧合钛(Ⅳ)的晶体结构与分子结构

本文报导了氧桥双核钛配合物[TiCl(BZBZ)_2]_2O的晶体结构和分子结构。配合物晶体(分子式C_(60)H_(44)Cl_2O_9Ti_2)属单斜晶系,C2/c空间群,a=21.013(7),b=18.509(2),c=17.493(2),β=91.43(2)°,V=6801.5(?)~3,M_r=1075.72,Z=4,D_x=1.05 gcm~(-3),μ=3.54 cm~(-1),F(000)=2216,R=0.104(1887个可观测衍射)。配合物分子由Ti—O—Ti桥氧骨架构成,有一分子内二重轴通过桥氧原子。对配合物的生成机理作了探讨。     

Reaction of 2-(4,5-dihydrofur-3-yl)-1,3-diphenyl-1,3-diaza-2-2λ3-phospholidine withC,N-diphenylnitriliminewithC,N-diphenylnitrilimine

The reaction of 2-(4,5-dihydrofur-3-yl)-1,3-diphenyl-1,3-diaza-2λ³-phospholidine withC,N-diphenylnitrilimine is a multistage process, in the course of which the 1,2,4-diazaphosphorine ring is formed and both rings of the initial organophosphorus compound are cleaved. 5-(2-Chloroethyl)-4-(N,N′-diphenylethylenediamino)-1,3-diphenyl-1,4-dihydro-1, 2,4λ⁵-diazaphosphorine was obtained as the final product. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–128, January, 2000.     

Synthesis and Structural Determination of (2R,4S,SS)-( )-Threo-5-(2,2-dichloroacetamido)-4-(4-nitrophenyl)-2-aryl-1,3-dioxanes

Acetalscanbesynthesizedinanumberofways.Themainproblemintheacetalformationinacidicmediumistoshifttheequilibriumtotherightbyremovalofthewaterformedduringthereactionl.Wesynthesized(2R,4S,SS)-( )-threo-5-(2,2-dich(4-nitrophenyl)-2-aryl-1,3-dioxanesbyacet...     

C59XH(X=N,B)与1,3-丁二烯Diels-Alder环加成反应的区域选择性

应用半经验的AM1和密度泛函B3LYP/6-31G*方法对1,3-丁二烯与C59XH(X=N, B) Diels-Alder环加成反应的区域选择性进行理论研究, 选择一些有代表性的C59XH(X=N, B)的6—6键探讨环加成反应的机理. 1,3-丁二烯与C59NH进行的Diels-Alder反应, 随着加成位置远离C59NH的N原子, 活化能越来越低, 但都比1,3-丁二烯与C60相应反应的活化能高. 与此相反, 对于1,3-丁二烯与C59BH进行的环加成反应, 加成位置最靠近B原子的2,12/r-和2,12/f-过渡态的势垒最低, 并且比1,3-丁二烯与C60进行环加成反应的活化能约低18 kJ·mol-1, 其产物也是热力学最稳定的. 与C60相应的反应相比, C59NH和C59BH中N和B原子不同的电子性质对其邻位双键进行Diels-Alder环加成反应的活性产生了不同影响, 前者使反应活性降低, 后者使反应活性增强.     

Binuclear cyclopalladated compounds with antitubercular activity: synthesis and characterization of [{Pd(C2,N-dmba)(X)}2(μ-bpp)] (X = Cl,Br, NCO,N3; bpp = 1,3-bis(4-pyridyl)propane)

Reactions between [Pd(C²,N-dmba)(μ-X)]₂ (Hdmba?=?N,N-dimethylbenzylamine; X?=?Cl, Br, NCO, N₃) and 1,3-bis(4-pyridyl)propane (bpp) in 1?:?1 molar ratio at room temperature resulted in the binuclear compounds [{Pd(C²,N-dmba)(X)}₂(μ-bpp)] (X?=?Cl (1), Br (2), NCO (3), N₃ (4)), which were characterized by elemental analyses, infrared (IR), ¹H- and ¹³C{¹H}-NMR spectroscopies, and thermogravimetric analysis. The IR and NMR data of 1–4 were consistent with the presence of bridging bpp. The thermal stability order of the complexes was 4?>?3?>?2?>?1. Compounds 1–4 and bpp were tested against Mycobacterium tuberculosis and their MIC values were determined.     

Synthesis and crystal structure of the molecular complex of fullerence C60 with 2-(4-thiono-1,3-dithiolan-5-ylidene)-4,5-dimethyl-1,3-diselenol (C60·2DTDS)

A new molecular complex of fullerene C₆₀ with 2-(4-thiono-1,3-dithiolan-5-ylidene)-4,5-dimethyl-1,3-diselenol (C₆₀·2DTDS) was synthesized for the first time. The crystal and molecular structures of C₆₀·2DTDS were established by X-ray diffraction analysis. The crystal structure of C₆₀·2DTDS is layered: the layers of fullerene C₆₀ molecules alternate with those of DTDS molecules. The molecules of C₆₀ and DTDS are associated by shortened C...Se, C...S, and C...C contacts forming a three-dimensional network of secondary interactions in the crystal. The C₆₀·2DTDS crystals have a specific feature: the absence of shortened C...C contacts between the nearest C₆₀ molecules despite the short distances between their centers, 9.948(2) and 10.054(2) Å. The electrochemical properties of DTDS were studied by cyclic voltammetry in CH₂Cl₂/0.05M Bu₄NPF₆ at room temperature. DTDS undergoes reversible one-electron reduction to a radical anion [E ^o=?1.81 V (Fc^0/+)] and reversible one-electron oxidation to a radical cation [E ^o=+0.37 V (Fc^0/+)]. The degree of charge transfer in C₆₀·2DTDS, ΔN=0.18, calculated from the electrochemical parameters of DTDS and C₆₀ indicates that this compound is a molecular complex with a partial charge transfer.     

Synthese,Struktur und Reaktivität von funktionalisierten Stibanidokomplexen des Eisens und Rutheniums [(η5-C5Me5)(CO)2MSbR1R2] (M = Fe,Ru; R1, R2 = SiMe3, C(O)tBu,C(O)Ph,C(O)-1 Ad)

Synthesis, Structure, and Reactivity of Functionalized Stibanido Complexes of Iron and Ruthenium [(η⁵-C₅Me₅)(CO)₂MSbR¹R²] (M = Fe, Ru; R¹, R² = SiMe₃, C(O) t Bu, C(O)Ph, C(O)-1 Ad) The reaction of equimolar amounts of [(η⁵-C₅Me₅)(CO)₂RuSb(SiMe₃)₂] ( 1 b ) and the carboxylic chlorides RC(O)Cl (R = tBu, Ph, 1-adamantyl) afforded the acyl(trimethylsilyl)stibanido complexes [(η⁵-C₅Me₅)(CO)₂RuSb · {C(O)R}(SiMe₃)] 2 b (R = tBu), 4 b (R = Ph), and 6 b (R = 1-Ad). The treatment of 1 b with two molar equivalents of pivaloyl chloride and benzoyl chloride led to the diacylstibanido complexes [(η⁵-C₅Me₅)(CO)₂RuSb{C(O)R}₂] ( 3 b , 5 b ). Analogously, the iron complex [(η⁵-C₅Me₅)(CO)₂FeSb · (SiMe₃)₂] ( 1 a ) is converted into the corresponding diacylstibanido complexes 3 a (R = tBu), 5 a (R = Ph) and 7 a (R = 1-Ad) by an excess of acid chloride. The treatment of 1 a with equimolar amounts of RC(O)Cl gave inseparable mixtures of starting material and the monoacyl- and diacyl stibanido complexes. Oxalyl chloride reacted quantitatively with two equivalents of 1 a to give complex [{(η⁵-C₅Me₅) · (CO)₂FeSb(SiMe₃)C(O)}₂] ( 8 ). The molecular structures of 1 a , 2 b and 5 b were elucidated by single crystal X-ray analyses.     

银配合物[Ag(OPOQ)](BF4)(OPOQ=O,O′-双(8-喹啉基)-1,3二氧丙烷)的合成与表征

四氟硼酸银和配体O,O′-双(8-喹啉基)-1,3-二氧丙烷(OPOQ)反应,生成标题配合物[Ag(OPOQ)](BF4) (C21H18AgBF4N2O2 , Mr = 525.05 ), 并通过了元素分析、红外光谱、核磁氢谱及X-单晶结构表征.配合物的晶体为单斜晶系,空间群为P21/n, 晶胞参数a = 12.009(6), b = 14.594(7), c = 12.124(6)(A); β= 111.875(8)(, V = 1972.0(17)(A)3,Dc = 1.769 g/cm3, Z = 4, ((MoKα) = 1.081 mm-1, F (000) = 1048, S = 1.066.最终偏离因子R = 0.0336, wR = 0.0414.晶体结构显示,该配合物的阳离子是一个半包围的弓形结构.     

Crystal structure of <Emphasis Type="Italic">N,N</Emphasis>′-Bis-(2,5-dimethoxybenzylidene)-1,3-diaminopropane

The Schiff-base compound N,N′-Bis-(2,5-dimethoxybenzylidene)-1,3-diaminopropan, (2,5-MeO-ba)₂pn, is synthesized and characterized by elemental analysis, FT-IR and ¹H NMR spectroscopy. The crystal structure of (2,5-MeO-ba)₂pn is determined by X-ray single crystal diffraction analysis. The X-ray diffraction analysis at 120 K reveals that (2,5-MeO-ba)₂pn crystallizes in the orthorhombic system, Fdd2 space group with a = 29.339(9) Å, b = 29.4073(11) Å, c = 4.4524(2) Å, V = 3840.8(3) ų, μ = 0.72 mm^?1, and Z = 8.