含硫帽的三核和四核钌羰基簇合物的合成和结构表征

The reaction of Ru₃(CO)₁₂ with five-membered cyclic SP(S)(Fc)N(Ph)NC(Me) gave two novel trinuclear and tetranuclear ruthenium carbonyl clusters containing capping S atoms in Ru₃(CO)₈(μ₃-S)₂[P(Fc)N(Ph)NC(Me)S] 1 and Ru₄(CO)₇(μ-CO)₃(μ₄-S)₂[P(Fc)N(Ph)NC(Me)S] 2 (Fc=C₅H₅FeC₅H₄). During the reaction, the ligand precursor cleaved only in its P=S bond to give the fragments S and [P(Fc)N(Ph)NC(Me)S], and then coordinated to the ruthenium atoms to form the clusters as listed above. The clusters have been characterized by elementary analysis, IR, ¹H NMR and MS spectroscopy. The crystal structure of cluster 2 has been determined by X-ary diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The unit cell parameters are as follows: a=1.18744(7) nm, b=1.36041(11) nm, c=2.20026(18) nm, β=104.126(3) °, V=3.4468(5) nm³, D_c=2.175 g·cm^-3, Z=4. In the molecule, the three bridging carbonyls and Ru4 are planar and with a pseudo-octahedral Ru₄S₂ skeleton. The terminal carbonyl of Ru1 was substituted by the cyclic ligand [P(Fc)N(Ph)NC(Me)S]. CCDC: 217076.     

双核银化合物:六乙烯基硫脲二高氯酸合银的合成和晶体结构

The crystal and molecular structure of [Ag₂(ETU)₆]·(ClO₄)₂ has been determined by X-ray crystallography. It crystallizes in the monoclinic, space group P2₁/c, with lattice parameters a=0.63270(9)nm, b=2.4264(2)nm, c=1.2128(1)nm, β=92.721(9)°, V=1.8597(3)nm³, Z=4, D_c=1.835Mg·m^-3, F(000)=1032, μ=1.591mm^-1. The molecule is built up of centro-symmetric dimeric entities, in which the four-membered Ag₂S₂ ring is planar and the angle of S(3)-Ag(1)-S(3A) is 107.70(2)° for symmetry requirements. The silver atoms have slightly distorted tetrahedral coordination environment, and the sulfur atoms of the ETU group occupy four coordi-nation sites. The two percholate anions in general position balance the charge. In the solid state, the title compound forms three dimensional network structures through hydrogen bonds. The intermolecular hydrogen bonds and ex-tensive intermolecular interaction connect the [Ag2(ETU)₆]²⁺ ion and two ClO₄^- anions to contribute to the stability of the structure. CCDC: 208731.     

梯形结构有机锡配合物{[(p-MeC6H4CH2)2Sn]2(O)(Cl)OC2H5}2的合成和晶体结构

The title compound {[(p-MeC₆H₄CH₂)₂Sn]₂(O)(Cl)OC₂H₅}₂ was synthesized by the reaction of bis(p-met-hylbenzyl)tin dichloride with KOH in ethanol. The crystal structure of the complex has been determined by X- ray diffraction. The crystal belongs to monoclinic, space group P2₁/c with a=1.114 0(19) nm, b=2.423 1(3) nm, c=2.521 1(3) nm, β=99.398(3)°, V=6.714(16) nm³, Z=4, D_c=1.493 g·cm^-3, μ(Mo Kα)=15.94 cm^-1, F(000)=3 024, R₁=0.049 9, wR=0.101 7. The crystal structure shows that the coordination geometry of tin is a distorted trigonal bipyramid, and the ladder-like structure is shaped by three Sn₂O₂ planar four-membered rings. CCDC: 639682.     

两个含铁、钴、硫金属异核羰基取代簇合物的合成及结构

Two novel substituted derivatives ( μ3-S)( μ-H)Fe₂Co(CO)₇L_n (n=2, L=AsPh₃ (3) n=1, L=dppm (4)) have been synthesized and characterized by IR, ¹H NMR, ³¹P NMR, MS and X-ray crystallography . The cluster 4 crystallizes in monoclinic space group C2/c, with a=1.589 1(7), b=1.814 9(8), c=2.277 8(11) nm, β=96.861(8), V=6.522(5) nm³, Z=8, D_c=1.552 g·cm^-3, F(000)=3 094, μ=12.95 cm^-1. Final R indices [i>2σ(I)]: R₁=0.054 3, wR₂=0.101 1. The cyclic voltammetric behavior for the parent cluster 1 and its substituted derivatives were investigated, the results show that the order of σ-donator ability is CO < PPh₃ < AsPh₃ < dppm. CCDC: 221867.     

[Pb2(TNR)(NO3)2(H2O)]的制备和晶体结构研究

[Pb₂(TNR)(NO₃)₂(H₂O)] was prepared by reaction of the aqueous solution of lead nitrate and magnesium styphnate. The crystal structure of Pb₂(TNR)(NO₃)₂(H₂O)was determined by single crystal diffraction analysis. The crystal is triclinic, space group P1 with crystal parameters a=0.7279(2)nm,b=1.0698(2)nm,c=1.0738(2)nm;α=86.82(1)°,β=89.52(2)°,γ=83.50(2)°;V=0.8295(3)nm³,Z=2,D_c=3.201g·cm^-3, F(000)=716. The final R value is 0.0358.In the crystal structure, one lead ion was represented by nine coor-dination geometry; the other was showed as ten coordination geometry.     

桥联双核配合物[(DPC)2Co2(H2O)5]·2H2O的合成与晶体结构

The new complex formulated [(DPC)₂Co₂(H₂O)₅]·2H₂O (HDPC^- is pyridine-2,6-dicarboxylate) has been synthesized and the crystal structure was determined by X-ray diffraction. The crystal structure of the complex belongs to monoclinic system with space group P2₁/c, a=0.83850(10) nm, b=2.7386(4) nm, c=0.9610(2) nm, β=98.280 (10) °, V=2.1838(6) nm³, Z=4, D_c=1.746 g·cm^-3, μ=1.597 mm^-1. In the crystal the two Co²⁺ are in distorted octahedrons. The part of [Co(DPC)₂] possess an approximate D_2d symmetry, while the part of [OCo₍₂₎(OH₂)₅] has an approximate C₂ symmetry.     

含叠氮酸根的锰(Ⅱ)配合物的合成与晶体结构

Two new mononuclear Mn(Ⅱ) complexes Mn(phen)₂(N₃)₂ (1) and [Mn(phen)₂(N₃)(H₂O)]ClO₄·H₂O (2) have been synthesized and structurally characterized, where phen is 1,10-phenanthroline. Complex 1 crystallizes in the P1 space group, with lattice parameters a=8.1688(2)?, b=11.1218(2)?, c=12.6881(2)?, α=83.558(3)°, β=82.287(3)°, γ=73.643(3)°, V=1092.7(4)?³, D_c=1.518Mg·m^-3, Z=2, F(000)=510, R₁=0.0620, wR₂=0.0958 (based on F²), S=0.981. Complex 2 crystallizes in the P1 space group, with lattice parameters a=8.6543(2)?, b=8.9767(2)?, c=17.5915(4)?, α= 93.399(3)°, β=102.806(3)°, γ=106.234(3)°, V=1268.7(4)?³, D_c=1.552Mg·m^-3, Z=2, F(000)=606, R₁=0.0672, wR₂=0.1781 (based on F²), S=1.047. In complex 1, the Mn atom is coordinated by six nitrogen atoms of two phen molecules and two N₃^- ions with the Mn-N distances ranging from 2.142(4) to 2.318(4)?. The coordinated phen molecules of the adjacent Mn(phen)₂(N₃)₂ moieties experience π-π stacking which is responsible for the crystal packing. In complex 2, the Mn atom is coordinated by five nitrogen atoms of two phen molecules and one N₃^- ion with the Mn-N distances ranging from 2.152(5) to 2.291(5)?. The approximately octahedral environment was completed by the oxygen atom of the coordinated water molecule with the Mn-O distance of 2.180(5)?. The hydrate water molecule is hydrogen-bonded to one of the O atoms of free ClO₄^- anion. ?     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.     

四元混配配合物[Ce(CH2=C(CH3)-COO)2(NO3)(phen)]2的合成、表征及晶体结构

A new complex with mixed-quadriligand [Ce(CH₂=C(CH₃)-COO)₂(NO₃)(phen)]₂ has been synthesized in aqueous solution of slight acidity and characterized by elementary analysis, IR and TGA. The crystal structure determination shows that the complex belongs to triclinic, space group P1, a=9.614?, b=10.047?, c=11.821?, Z=2, α=100.88(3)°, β=106.29(3)°, γ=97.93(2)°, V=1054(5)?³, D_c=1.741g·cm^-3, F(000)=546.00, μ(MoKα)=22.06cm^-1. And the crystal is consisted of a binuclear molecule. The coordina-tion of Ce³⁺ is nine.     

一种镧系-过渡金属二维氰桥配合物[Nd(DMSO)2(H2O)2][Ni(CN)4]Cl(DMSO=二甲亚砜)的合成和晶体结构(英)

The cyano-bridged bimetallic complex [Nd(DMSO)₂(H₂O)₂][Ni(CN)₄]Cl with two-dimensional gridding molecule structure was synthesized and characterized. In the complex all four cyano groups of unit Ni(CN)₄^2- are bound to Nd³⁺ ions. The crystal data for the title complex: monoclinic, space group P2₁/c, a=0.780 0(3) nm, b=1.509 7(6) nm, c=1.683 2(6) nm, β=115.231(14)°, Z=4, μ=4.311 mm^-1, final R₁=0.020 9, wR₂=0.045 4. CCDC: 272214.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.