2(3 H)呋喃酮向2(5 H)呋喃酮的转化研究

本文研究2(3H)呋喃酮的热转化和碱催化成2(5H)呋喃酮的过程。应用NMR跟踪技术测定了转化动力常数, 计算了活化能, 这对确定适宜的转化条件具有实际指导意义。还对碱催化下的转化机理进行了探讨。     

The Structure of Pd2(CH≡CC6H5)2(C5H7O2)3(BF3)2BF4

IR and NMR data showed that the ionic complex Pd₂(CHCC₆H₅)₂(C₅H₇O₂)₃(BF₃)₂BF₄ isolated in the reaction Pd(Acac)₂ + PA + 5BF₃OEt₂ (Acac is C₅H₇O₂, PA is phenylacetylene) is an adduct of two complexes, namely, (Acac)PdBF₄ and [(PA)₂Pd(C³-Acac · BF₃)]⁺(Acac · BF₃)^– (coordinatively unsaturated). On dissolution in deuteroacetone or deuteromethanol, the [(Acac)PdF₂BF₂Pd(C³-Acac · BF₃)(PA)₂]⁺(Acac · BF₃)^– adduct decomposed to Pd(Acac)₂, 2BF₃ · L (L = (CD₃)₂CO, CD₃OD) and the [L(PA)₂Pd(C³-Acac]⁺BF₄ ^– complex.     

Structure of (C3H5NH3)2H2P2O7·H2O

The bis(cyclopropylammonium)dihydrogenodiphosphate monohydrate is a new diphosphate associated with the organic molecule C₃H₅NH₂. We report the chemical preparation and the crystal structure of this organic cation diphosphate. (C₃H₅NH₃)₂H₂P₂O₇.H₂O is orthorhombic (S.G. : P2₁2₁2₁), with Z = 4 and the following unit-cell parameters : a = 4.828(1) Å, b = 11.011(1) Å, c = 25.645(2) Å. The P₂O₇ groups and H₂O water molecules form a succession of bidimensional layers perpendicular to the c axis. The organic cations ensure the three-dimensional cohesion by NH-O hydrogen bonds.     

Substitution and insertion reactions of (η5-C5H5)Cr(CO)3C2H5

The complex (η⁵-C₅H₅)Cr(CO)₃Cp42 H₅ has been made and its reactions with σ donor ligands L (L = (MeO)₃P and (EtO)₃P) and with SO₂ studied. The alkyl phosphites give compounds of the composition (η⁵-C₅H₅)Cr(CO)₂LC₂H₅, and sulfur dioxide gives the corresponding S-sulfinato (η⁵-C₅H₅)Cr(CO)₃SO₂C₂H₅.     

Efficient Diastereoselective Synthesis of Chiral Diferrocenylphosphine‐diamines: X‐ray Crystal Structure of [(η5‐C5H5)Fe{(η5‐C5H3)PPh2CH(CH3) N(CH2)2(CH2)2NCH(CH3)PPh2 (η5‐C5H3)}Fe(η5‐C5H5)]

Abstract

Three novel chiral planar diferrocenylphosphine‐diamines 5 (a–c) were designed and synthesized starting with (s)‐(?)‐N,N‐dimethyl‐1‐ferrocenylethylamine‐1 [(S)‐1]. All new compounds were identified by ¹H NMR and MS. The structure of chiral diferrocenylphosphine‐diamine 5c was determined by X‐ray crystallography. Single crystal X‐ray diffraction analysis reveals that the molecular structure of compound 5c [(η⁵‐C₅H₅)Fe{(η⁵‐C₅H₃)PPh₂CH(CH₃) N(CH₂)₂(CH₂)₂NCH(CH₃)PPh₂‐(η⁵‐C₅H₃)}Fe(η⁵‐C₅H₅)] is enantiomerically pure and crystallizes in the noncentrosymmetric P2(1)2(1)2(1) space group; it maintains “Z” shape and contains a piperazine hexahydrate ring bridge. The piperazine ring adopts a favored chair conformation and the chiral center C₂₃ and C₂₉ substituents in S‐configuration.     

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) ?, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) ?(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) ?, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) ?(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not significantly couple with the S = 1/2 vanadyl groups. The susceptibility data can be successfully reproduced assuming a distorted ligand field for the Co(2+) ions (1) and an O(h)-symmetric Ni(2+) ligand field (2).     

(C5H5)2NdCl·2LiCl 与正丁基锂的反应: [Li(DME)3][(C5H5)3Nd(μ-H)Nd(C5H5)3]的合成及其晶体结构

研究了(C5H5)2NdCl·2LiCl与正丁基锂在THF溶液中的反应, 并从该反应液中分离到了钕的氢化物[Li(DME)3][(C5H5)3Nd(μ-H)Nd(C5H5)3] 1. 化合物1经X射线单晶结构测定表明属单斜晶系, 空间群P21/c, 晶胞参数为a=0.9670(2) nm, b=2.1001(5) nm, c=2.1279(7) nm, β=90.89(2)°, Z=4, V=4.321 (2) nm3, Mr=957.36, Dc=1.47 g·cm-3, F(000)=1936, R=0.094, wR=0.100. 1的晶胞中包含两个独立的晶体分子, 每一分子由阴阳离子对[Li(DME)3]+和[(C5H5)3Nd(μ-H)Nd(C5H5)3]-组成. 钕原子与3个η5-C5H5基团配位, 且两个(C5H5)3Nd经氢桥键相连构成阴离子. Nd1-H和Nd2-H键长均为0.218(1) nm.     

Coordination-unsaturated complexes of tris(cyclopentadienyl)samarium: Solvate (η5-C5H5)3Sm·OC4H8 and ionic salt [Li(Et2O)2][η5-C5H5)3Sm(μ-Cl)Sm(η5-C5H5)3]

X-ray structural analysis of a samarium triscyclopentadienyl complex, Cp₃Sm·OC₄H₈ (1), and a samarium ionic salt, [Li(Et₂O)₂][Cp₃Sm(-Cl)SmCp₃] (2), was carried out. In both compounds coordination saturation is achieved by coordination of the THF molecule (in1) or the Cl^– anion (in2) to the monomeric fragment Cp₃Sm. An unusual coordination of the Li⁺ cation was observed in complex2: it is bound to one of the ⁵-type cyclopentadienyl rings in addition to two ether molecules.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1129–1132, June, 1993.     

Synthesis and structure of a three-dimensional lanthanide complex [Tm2(C5H3N(COO)2)3(H2O)3)]·H2O

A new three-dimensional complex [Tm₂(C₅H₃N(COO)₂)₃(H₂O)₃)]·H₂O (PDC?=?3,5-pyridinedicarboxylate), has been synthesized and its structure determined by x-ray single crystal diffraction methods. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a?=?14.579(4), b?=?11.193(3), c?=?14.839(5)?Å, β?=?94.009(6)°, U?=?2415.5(13)?ų. Two independent PDC ligands bridge Tm^III ions from different orientations to form a network. Thermogravimetric analyses on compound 1 show its high structural stability to 410°C.     

Infrared investigations of the order–disorder ferroelectric phase transitions in imidazolium halogenobismuthates(III) and halogenoantimonates(III): (C3N2H5)5Bi2Cl11, (C3N2H5)5Bi2Br11 and (C3N2H5)5Sb2Br11

Infrared spectra of the powdered (C₃N₂H₅)₅Bi₂Cl₁₁, (C₃N₂H₅)₅Bi₂Br₁₁and (C₃N₂H₅)₅Sb₂Br₁₁ crystals in the region of internal vibrations of the imidazolium cations (3600 and 400 cm⁻¹) at the temperature intervals of 10–300 K, covering paraelectric–ferroelectric phase transitions, are presented and discussed in this paper. The research shows that the vibrational states of the imidazolium cations change markedly during the paraelectric–ferroelectric phase transition. The continuous nature of these transitions is well reflected in the infrared spectra, which is consistent with the previous X-ray and dielectric findings.     

Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

Synthesis and structures of the η5-C5H5Cl(CO)2W-η1,η5-(PPh2)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 and MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3 complexes

The metallation of the η⁵-C₅H₅(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex with BuⁿLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph₂PCl afforded the η⁵-Ph₂PC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex. The reaction of the latter with η⁵-C₅H₅(CO)₃WCl in the presence of Me₃NO produced the trinuclear complex η⁵-C₅H₅Cl(CO)₂W-η¹,η⁵-(Ph₂P)C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃. The structure of the latter complex was established by IR, UV, and 1H and ³¹P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl₃ with three equivalents of LiC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃ gave the hexanuclear complex MeSi[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃]₃.     

Unique seven-node rare-earth octacyanomolybdate(IV) three-dimensional molecular frameworks: {[Er(H2O)5(Er(H2O)4)3][Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu(H2O)4)3][Mo(CN)8]3·11H2O}n

The crystal structure analyses of {[Er(H₂O)₅(Er(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (1) and {[Eu(H₂O)₅(Eu(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (2), show that they are not only new neutral three-dimensional rare-earth octacyanomolybdate(IV) molecular frameworks, but that they also belong to an unknown structure type having seven different nodes. To the best of our knowledge this is different to any other known molybdenum(IV) octacyanide complexes published to date. Both compounds crystallize in the triclinic system, space group P-1, and are isostructural and isotypic. The coordination polyhedra of the molybdenum atoms in the three different [Mo(CN)₈]⁴⁻ anions are trigonal prisms, with two additional atoms. A new bridging mode for octacyanometallates is also observed with five of the eight cyanide groups involved in bridging either three or four rare-earth atoms, while the three remaining cyanide groups are terminal and are involved in hydrogen bonding. The four rare-earth atoms in 1 and 2 have different coordination polyhedra in the form of trigonal prisms with two additional atoms. The three-dimensional structures are made up of infinite two-dimensional slabs linked by one of the rare-earth metal atoms. In both compounds, apart from the 17 coordinated water molecules, there are 11 lattice water molecules of crystallization present in the cavities of the three-dimensional frameworks. The 28 water molecules and the terminal CN⁻ groups are involved in an extensive O–H⋯O and O–H⋯N hydrogen bonding network.     

Synthese des Metallosulfins π-C5H5(CO)2FeC(SCH3)SO durch gezielte S-Oxidation der Thiocarbonyl-Funktion von π-C5H5(CO)2FeC(S)SCH3

Abstract

Der Methylester des Metallodithiocarboxylats π-C₅H₅(CO)₂FeC(S)SCH₃ wird durch 3-Chlorper-benzoesäure, 3-ClC₆H₄CO₃H, am Schwefelatom der Thiocarbonylfunktion zum Metallosulfin π-C₅H₅(CO)₂FeC(SCH₃)SO oxidiert, dessen Struktur und E-Konfiguration aus einem Vergleich der spektroskopischen Daten von Edukt, Produkt und analogen Metallosulfinen resultiert.

The methylester of the metallodithiocarboxylate π-C₅H₅(CO)₂FeC(S)SCH₃ is oxidized by 3-chlorperbenzoic acid, 3-ClC₆H₄CO₃H, at the sulfur atom of the thiocarbonyl function to give the metallosulfine π-C₅H₅(CO)₂FeC(SCH₃)SO; its structure and E-configuration derives from comparison of the spectroscopic data of educt, product and analogous metallosulfines.     

The addition of small molecules to (η-C5H5)2Rh2(CO)(CF3C2CF3): IV. The sunlight assisted making and breaking of alkene CH bonds on the dirhodium centre; the crystal and molecular structures of (η-C5H5)2Rh2(CHCHCN){C(CF3)CF3)H} · H2O and (η-C5H5)2Rh2(CHCF2){C(CF3)C(CF3)H}

Bis-alkenyl complexes of the type (η-C₅H₅)₂RH₂(alkene − H)(alkyne + H) are obtained when the alkyne complex (η-C₅H₅)₂Rh₂(CO)(CF₃C₂CF₃) is treated with the following alkenes: H₂CCH₂, H₂CCHR (R = Me, Bu^t, Ph, CN), H₂CCF₂, RHCCHR′ (R = R′ = Me, Ph, Cl; R = Me, R′ = Et), cyclooctene and norbornene. An approximately equimolar amount of (η-C₅H₅)₂Rh₂(CO)₂(CF₃C₂CF₃) is also formed. The reactions are greatly accelerated when the reaction mixtures are exposed to sunlight. There is some regioselectivity in the reactions with H₂CCHR and MeHCCHet, with a preference for CH bond cleavage at the least crowded alkene-carbon. When the reaction with acrylonitrile is performed in the absence of sunlight, the complex (η-C₅H₅)₂(CO){(H₂CCHCN)(CF₃C₂CF₃)} can be isolated; upon exposure to sunlight, there is loss of CO and H-transfer to form two isomers of the appropriate bis-alkenyl complex.The molecular geometries of (η-C₅H₅)₂Rh₂(CHCHCN){C(CF₃)C(CF₃)H} and (η-C₅H₅)₂Rh₂(CHCF₂){C(CF₃)C(CF₃)H} have been ascertained by X-ray structure determination. Each molecule has two bridging alkenyl units spanning a RhRh single bond; the dihedral angle between the two RhRhCC planes is just above 90°. There is a cyclopentadienyl ring η⁵-attached to each metal. Crystal data: C₁₇H₁₃F₆NRh₂·H₂O, M 569.1, monoclinic, P2₁/n, a 15.014(7), b 14.882(7), c 8.590(5) Å, β 94.57(9)°, Z = 4, final R 0.056 for 2493 observed reflections; C₁₆H₁₂F₈Rh₂, M 562.1, monoclinic, P2₁/c, a 13.037(6), b 8.765(2), c 14.873(3) Å, β 103.16(3)°, Z = 4, final R 0.062 for 1820 observed reflections.     

Structural study of complex [Rh(NH3)5(NO2)](NO3)2·H2O, [Rh(NH3)5(NO2)][Pd(NO2)4], and K2[Rh(NH3)(NO2)5]·H2O salts

Compounds [Rh(NH₃)₅(NO₂)](NO₃)₂·H₂O (I) with a = 7.6230(3) Å, b = 7.6230(3) Å, c = 10.3584(4) Å, space group I-42m, Z = 2, d _calc = 2.026 g/cm³, V = 601.93(4) ų, Rh-NH_{3 eq} = 2.074 Å, Rh-NH_{3 ax} (NO₂) = 2.048 Å; [Rh(NH₃)₅(NO₂)][Pd(NO₂)₄] (II) with a = 8.095(3) Å, b = 22.422(8) Å, c = 7.887(3) Å, β = 98.559(17)°, space group Cc, Z = 4, d _calc = 2.461 g/cm³, V = 1415.6(9) ų, Rh-NH_{3 eq} = 2.069 Å, Rh-NH_{3 ax} = 2.090 Å, Rh-NO₂ = 2.002 Å; K₂[Rh(NH₃)(NO₂)₅]·H₂O (III) with a = 7.5177(5) Å, b = 20.9856(15) Å, c = 7.7017(5) Å, space group Cmc2₁, Z = 4, d _calc = 2.439 g/cm³, V = 1215.05(14) ų, Rh-NH_{3 ax} (NO₂) = 2.094 Å, Rh-NO_{2 eq} = 2.030 Å are synthesized and studied using single crystal X-ray diffraction.     

Structure and Catalytic Activity of Nickel-substituted Mica- montmorillonite Clay Crosslinked with NH2(C3H3)Si(OC2H5)2

Nickel-substituted mica-montmorillonite clays(Ni-SMM) were synthesized, the pillared clays, Si-Ni-SMM, were prepared from the Ni-SMM intercalated with NH2(C3H5)Si(OC2H5)3.The pillar perhaps consists of tripolymer of silica according to the judgement from the pillar height (8. 5A ) data. The results of IR, ESR and XRD indicate that the hydroxy group in the octahedral layer is attacked by crosslinking agent. Thus the silicon oxide pillars become directly linked via oxygen to the nickel atoms in the octahedral layer. The change of the ratio of Lewis to Bronsted acidity on Si-Ni-SMM reduced at 400℃ by H2 shows that the hydrogenating component such as Ni in the framework of SMM plays an important role in catalyst deactivation in H, atmosphere. This kind of action may be due to spilled- over hydrogen.     

Tantalocene complexes as bidentate métalloligands: (C5Me5)(C5H4X)Ta(H2)(PPh2) (C5Me5) (C5H4X)Ta(CO) (PPh2) (X = PPh2, CH2CH2NMe2)

The synthesis of new bidentate métalloligands derived from tantalocene(C₅Me₅)(C₅H₄X)Ta(H₂)(PPh₂) (X = PPh₂, 2P; X = CH₂CH₂NMe₂2N) and (C₅Me₅)(C₅H₄X)Ta(CO)(PPh₂) 4(P,N) is described. When opposed to chromium unsaturated fragments the phosphino functionalised complexes 2P and 4P act as chelating bidentate ligands affording Ta(V) (C₅Me₅)(C₅H₄PPh₂)Ta(CH₂) (μ-PPh₂)Cr(CO)₄ or Ta(III) (C₅Me₅)(C₅H₄PPh₂)Ta(CO)(μ-PPh₂)Cr(CO)₄ bimetallic complexes. The same reaction carried out starting from 2N gives rise to a μ-phosphido, μ-hydrido dibridged complex Cp*(C₅H₄CH₂CH₂NMe₂)TaH(μ-H)(μ-PPh₂)Cr(CO)₄.