Synthesis of the first difunctional N-fluoro perfluoroalkylsulfonylimides, CF3SO2NFSO2(CF2)nSO2NFSO2CF3

Synthesis of difunctional N,N′-difluoro perfluoroalkylsulfonamides, CF₃SO₂NFSO₂(CF₂)_nSO₂NFSO₂CF₃, where n=4, 6 is reported. A related compound with an oxygen linkage CF₃SO₂NFSO₂(CF₂)₂O(CF₂)₂SO₂NFSO₂CF₃ has also been prepared. These reagents showed good activity for electrophilic fluorination.     

IBX/n-Bu4NBr/CH2Cl2-H2O: a new mild system for selective oxidation of secondary alcohols

A new alternative system for the chemoselective oxidation of secondary hydroxyl group to ketone with IBX/n-Bu₄NBr in CH₂Cl₂-H₂O has been developed. Under the reaction conditions, the secondary hydroxyl group was highly chemoselectively oxidized to the corresponding ketone, in moderate to good yields at rt, in the presence of primary hydroxyl group within the same molecule.     

Structural and physical properties of the new intermetallic compound Yb3Pd2Sn2

The crystal structure of the ternary intermetallic compound Yb₃Pd₂Sn₂ has been determined ab initio from powder X-ray diffraction data. The compound crystallizes as a new structure type in the orthorhombic space group Pbcm and lattice constants a=0.58262(3), b=1.68393(8), c=1.38735(7) nm. Yb₃Pd₂Sn₂ is composed of a complex _∞[Pd₂Sn₂]^δ− polyanionic network in which the Yb ions are embedded. A comparison between this structure and those of Eu₃Pd₂Sn₂ and Ca₃Pd₂Sn₂, other novel polar intermetallic compounds, was made. DC susceptibility and ¹⁷⁰Yb Mössbauer spectroscopic measurements indicate a close-to divalent Yb behavior. Moreover, a hybridization between 4f and conduction electrons is suggested by electronic structure calculations and heat capacity measurements.     

Efficient cleavage of carboxylic tert-butyl and 1-adamantyl esters, and N-Boc-amines using H2SO4 in CH2Cl2

A new procedure for the deprotection of carboxylic tert-butyl and 1-adamantyl esters, and N-Boc-amines using H₂SO₄ in CH₂Cl₂ is described. The proposed method is simple, cheap, eco-friendly and represents a valid alternative to existing ones, with special significance in large scale applications.     

Synthesis, X-ray crystal structure and vibrational spectroscopy of the acidic pyrophosphate KMg0.5H2P2O7·H2O

The hydrated potassium hemimagnesium dihydrogen pyrophosphate KMg_0.5H₂P₂O₇·H₂O was synthesized. It crystallizes in the triclinic system, space group (n. 2), Z=2, with the following unit-cell parameters: a=6.8565(2) Å, b=7.3621(3) Å, c=7.6202(3) Å, α=81.044(2)°, β=72.248(2)°, γ=83.314(3)°, V=360.90(2) Å³. The structure was obtained by single-crystal X-ray diffractometry, and a full-matrix least-squares refinement based on F² gave a final R index of =0.0368 (wR=0.0975), utilizing 1446 observed reflections with I>2σ(I). The crystal packing consists in a three-dimensional network made by layers parallel to ab plane of PO₄ double tetrahedra and MgO₆ octahedra, linked by hydrogen bonds, while K atoms form complex coordination within cavities between tetrahedra and octahedra. The dihydro-pyrophosphate anion (H₂P₂O₇)²⁻ shows bent eclipsed conformation and the Mg²⁺ ion lies on inversion center. No coincidences observed between most of infrared and Raman spectral bands confirmed the centrosymmetric structure of the title compound; the vibrational spectra point to a bent POP bridge angle.     

Cleavage of alkoxycarbonyl protecting groups from carbamates by t-BuNH2

An efficient, simple protocol for the selective cleavage of a variety of N-alkoxycarbonyl protecting groups by t-BuNH₂/MeOH is described. The scope of the procedure was explored for a series of indole, aniline and pyrrolidine carbamate derivatives containing other potentially reactive functional groups affording a clean cleavage of the carbamate group.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

V2Cu3Ga8, Mo2Cu3Ga8 and W2Cu3Ga8—New compounds with a novel order variant of a bcc packing and motifs of self-similarity

Single crystals of the new compounds TM₂Cu₃Ga₈ (TM=V, Mo, W) were synthesised from the elements. Structure determinations of the isotypic compounds (cI104, space group , Z=8; Mo₂Cu₃Ga₈: a=11.9171(10) Å, 613 refl., 23 param., R₁(F)=0.022, wR₂(F²)=0.047; W₂Cu₃Ga₈: 11.9248(8) Å, 346 refl., 23 param., R₁(F)=0.048, wR₂(F²)=0.086; V₂Cu₃Ga₈: 11.7861(14) Å, 374 refl., 24 param., R₁(F)=0.033, wR₂(F²)=0.081) showed a new cubic structure type which can be classified as an ordered defect variant of a bcc packing with a^′=4a: [(TM)₂(Cu)₃(□)₃][Ga₈]. The coordination polyhedra of the transition metals consist of Ga₈-cubes with 3 sides capped by Cu leading to coordination number 11. The arrangement of the TMGa₈Cu₃-polyhedra is in a way they form itself a 3-fold capped cube. All compositions were confirmed by EDX measurements.     

Preparation, spectroscopic properties of 1,4-di (N,N-diisopropylacetamido)-2,3(1H,4H)-quinoxalinedione (L) lanthanide complexes and the supramolecular structure of [Nd2L2(NO3)6(H2O)2]·H2O

The reaction of lanthanide nitrate with 1,4-di (N,N-diisopropylacetamido)-2,3(1H,4H)-quinoxalinedione (L) yields six novel Ln(III) complexes ([Ln₂L₂(NO₃)₆(H₂O)₂]·H₂O) which are characterized by elemental analysis, thermogravimetric analysis (TGA), conductivity measurements, IR, electronic and ¹H NMR spectroscopies. A new quinoxalinedione-based ligand is used as antenna ligand to sensitize the emission of lanthanide cations. The lowest triplet state energy level of the ligand in the nitrate complex matches better to the resonance level of Eu(III) and Sm(III) than Tb(III) and Dy(III) ion. The f-f fluorescence is induced in the Eu³⁺ and Sm³⁺ complexes by exciting into the π-π* absorptions of the ligand in the UV. Furthermore, the crystal structures of a novel binuclear complex [Nd₂L₂(NO₃)₆(H₂O)₂]·H₂O has been determined by single-crystal X-ray diffraction. The binuclear [Nd₂L₂(NO₃)₆(H₂O)₂]·H₂O complex units are linked by the intermolecular hydrogen bonds and π-π interactions to form a two-dimensional (2-D) layer supramolecule.     

Pd2dba3/P(i-BuNCH2CH2)3N: a highly efficient catalyst for the one-pot synthesis of trans-4-N,N-diarylaminostilbenes and N,N-diarylaminostyrenes

A Pd₂dba₃/P(i-BuNCH₂CH₂)₃N catalyzed one-pot synthesis of unsymmetrically substituted trans-4-N,N-diarylaminostilbenes and both symmetrically and unsymmetrically substituted N,N-diarylaminostyrene derivatives is reported. The procedure involves two or more palladium catalyzed sequential coupling reactions (an amination and an inter-molecular Heck reaction) in one-pot using the same catalyst system with two different aryl halides, including aryl chlorides and hetero aryl halides as the coupling partners.     

New effective reagent [Cp2ZrH2 · ClAlEt2]2 for alkene hydrometallation

New bimetallic complex [Cp₂ZrH₂ · ClAlEt₂]₂ (1) was synthesized, and its reactivity in hydrometallation reaction with the following alkenes was studied: hept-1-ene, okt-1-ene, α-methylstyrene, (1S)-β-pinene, (+)-camphene. Complex 1 shows the highest reactivity among the other known Al,Zr-bimetallic complexes: [Cp₂ZrH₂ · ClAlBuⁱ₂]₂ (2), [Cp₂ZrH₂ · AlEt₃]₂ (3), [Cp₂ZrH₂ · AlBuⁱ₃]₂ (4) and [Cp₂ZrH₂ · HAlBuⁱ₂] (5) as well as organoaluminium compounds (OAC): ⁱBu₂AlH, ⁱBu₃Al and ⁱBu₂AlCl in presence of Zr catalysts. Chlorine containing complexes 1 and 2 appear to be more effective in alkene hydrometallation, and relative hydrometallation rates are (1S)-β-pinene ? (+)-camphene < α-methylstyrene < oct-1-ene < hept-1-ene. Hydrometallation of (1S)-β-pinene and its subsequent oxidation with I₂ run with high diastereoselectivity and yield trans-myrtanol. However, the diastereoselectivity of (+)-camphene hydrometallation is less than that for (1S)-β-pinene, and the reaction gives predominately endo-camphanol.     

Synthesis and structural investigation of the compounds containing HF2 anions: Ca(HF2)2, Ba4F4(HF2)(PF6)3 and Pb2F2(HF2)(PF6)

Three new compounds Ca(HF₂)₂, Ba₄F₄(HF₂)(PF₆)₃ and Pb₂F₂(HF₂)(PF₆) were obtained in the system metal(II) fluoride and anhydrous HF (aHF) acidified with excessive PF₅. The obtained polymeric solids are slightly soluble in aHF and they crystallize out of their aHF solutions. Ca(HF₂)₂ was prepared by simply dissolving CaF₂ in a neutral aHF. It represents the second known compound with homoleptic HF environment of the central atom besides Ba(H₃F₄)₂. The compounds Ba₄F₄(HF₂)(PF₆)₃ and Pb₂F₂(HF₂)(PF₆) represent two additional examples of the formation of a polymeric zigzag ladder or ribbon composed of metal cation and fluoride anion (MF⁺)_n besides PbF(AsF₆), the first isolated compound with such zigzag ladder. The obtained new compounds were characterized by X-ray single crystal diffraction method and partly by Raman spectroscopy. Ba₄F₄(HF₂)(PF₆)₃ crystallizes in a triclinic space group P1¯ with a=4.5870(2) Å, b=8.8327(3) Å, c=11.2489(3) Å, α=67.758(9)°, β=84.722(12), γ=78.283(12)°, V=413.00(3) Å³ at 200 K, Z=1 and R=0.0588. Pb₂F₂(HF₂)(PF₆) at 200 K: space group P1¯, a=4.5722(19) Å, b=4.763(2) Å, c=8.818(4) Å, α=86.967(10)°, β=76.774(10)°, γ=83.230(12)°, V=185.55(14) ų, Z=1 and R=0.0937. Pb₂F₂(HF₂)(PF₆) at 293 K: space group P1¯, a=4.586(2) Å, b=4.781(3) Å, c=8.831(5) Å, α=87.106(13)°, β=76.830(13)°, γ=83.531(11)°, V=187.27(18) Å³, Z=1 and R=0.072. Ca(HF₂)₂ crystallizes in an orthorhombic Fddd space group with a=5.5709(6) Å, b=10.1111(9) Å, c=10.5945(10) Å, V=596.77(10) Å³ at 200 K, Z=8 and R=0.028.     

Two tantalum fluorides templated with tren: [H4tren](TaF7)2·H2O and [H4tren](TaF7)2

Using tris(2-aminoethyl)amine [(C₂H₄NH₂)₃N] (tren) as a template, two new tantalum fluorides are obtained by slow evaporation of solutions: [H₄tren](TaF₇)₂·H₂O (I) and [H₄tren](TaF₇)₂ (II). The structure determinations are performed by single crystal X-ray technique. Structures of I and II are built up from isolated TaF₇ distorted monocapped trigonal prisms or pentagonal bipyramids; charge balance is achieved by tetraprotonated [H₄tren]⁴⁺ cations which possess a “scorpion” configuration. In I and II, TaF₇ polyhedra, connected by hydrogen bonds with water molecules in I, lie in corrugated layers; hydrogen bond networks ensure the cohesion between these layers and [H₄tren]⁴⁺cations.     

Structure and magnetic properties of RE2Cu2Cd

The ternary intermetallic compounds RE₂Cu₂Cd (RE=Y, Sm, Gd-Tm, Lu) were synthesized by induction-melting of the elements in sealed tantalum tubes. The samples were characterized by X-ray powder diffraction. The structure of Gd₂Cu₂Cd was refined from single crystal X-ray diffractometer data: Mo₂FeB₂ type, space group P4/mbm, a=756.2(3), c=380.2(3) pm, wR2=0.0455, 321 F² values, 12 variables. The structures are 1:1 intergrowth variants of slightly distorted CsCl and AlB₂ related slabs of compositions RECd and RECu₂. The copper and cadmium atoms build up two-dimensional [Cu₂Cd] networks (257 pm Cu-Cu and 301 pm Cu-Cd in Gd₂Cu₂Cd) which are bonded to the rare earth atoms via short RE-Cu contacts (290 pm in Gd₂Cu₂Cd). Temperature dependent susceptibility measurements of RE₂Cu₂Cd with RE=Gd, Tb, Dy, and Tm show experimental magnetic moments which are close to the free RE³⁺ ion values. The four compounds show ferromagnetic ordering at T_C=116.7(2), 86.2(3), 48.4(1), and 14.5(1) K, respectively, as confirmed by heat capacity measurements. Dy₂Cu₂Cd shows a spin reorientation at T_N=16.9(1) K.     

[H2en]2{La2M(SO4)6(H2O)2} (M=Co, Ni): First organically templated 3d-4f mixed metal sulfates

The first organically templated 3d-4f mixed metal sulfates, [H₂en]₂{La₂M(SO₄)₆(H₂O)₂} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediamine cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions).     

Acyl-platinum(II) and -palladium(II) complexes derived from 2-hydroxybenzaldehyde derivatives. X-ray structure of [Pt(OC6H4CO) (P(p-CH3C6H4)3)2]

Platinum(II) and palladium(II) complexes containing chelating acyl ligands have been synthesized from salicylaldehyde, 2-hydroxynaphthaldehyde and 2-hydroxy-3-methoxybenzaldehyde. The platinum(II) complexes [Pt(acyl)L₂], acyl  OC₆H₄CO, OC₁₀H₆CO, O(m-CH₃OC₆H₃CO), L  tertiary phosphine, 1/2 diphenylphosphinoethane, can be isolated with both monodentate and chelating diphosphines, whereas for palladium only the compounds with chelating phosphines are readily obtainable. The reactions of [Pt(OC₆H₄CO)L₂] with HCl afford trans-[PtCl(OHC₆H₄CO)L₂], L  monodentate tertiary phosphine and cis-[PtCl(OHC₆H₄CO)L₂], L2  1,2-bis-diphenylphosphinoethane, in which the metal—carbon bond remains intact. The structure of [Pt(OC₆H₄CO)-(P(p-CH₃C₆H₄)₃)₂] has been determined by X-ray diffraction methods and found to have the expected square planar structure. Some relevant bond lengths and angles are: PtP; 2.271(4) and 2.348(5) Å; PtC; 1.96(2) Å and PtO; 2.07(1) Å; PPtP  101°, CPtO  82°.     

Synthesis of meso-furyl porphyrins with N4, N3S, N2S2 and N3O porphyrin cores

A series of meso-furyl porphyrins with four different porphyrin cores (N₄, N₃S, N₂S₂ and N₃O) were synthesized and characterized. The comparison of NMR, optical and fluorescence properties of meso-furyl porphyrins with porphyrins with six-membered aryl groups indicates that electronic properties of porphyrins were changed drastically on the introduction of furyl groups at meso positions. The maximum shifts in spectral bands were observed for meso-furyl porphyrins with N₂S₂ core. On protonation, the absorption bands of meso-furyl porphyrins were further red shifted. All these changes were ascribed to the possibility of more planarity of the meso-furyl porphyrins due to the small size of the furyl groups which results in extending the π-delocalisation of the porphyrin ring in to the furyl groups.     

Intercalation behavior of n-alkylamines into an A-site defective layered perovskite H2W2O7

Intercalation behavior of n-alkylamines into a protonated form of an A-site defective layered perovskite H₂W₂O₇ has been investigated. Results from XRD indicate these materials are layered with the corresponding interlayer spacing governed by the n-alkylamine chain length, and a reversible intercalation and deintercalation property is observed among these intercalation compounds. The IR spectra of the intercalation compounds with n-alkylamines clearly show that n-alkyl chains possess an all-trans conformation, and H₂W₂O₇ accommodate n-alkylamines (C_nH_2n+1NH₂: n=3, 4, 7, 8, 12, 16) to form intercalation compounds via an acid-base mechanism. A linear relationship between the interlayer distance and the number of carbon atoms in n-alkyl chains is observed to show a bilayer arrangement of the n-alkyl chains with a tilt angle of ∼71.6°. Elemental analysis studies reveal that the amounts of intercalated n-alkylamines are about 2.0 mol per [W₂O₇]. Despite the surface geometry of H₂W₂O₇ is almost identical to those of layered perovskites H₂[A_n−1B_nO_3n+1], the amounts of intercalated n-alkylamines of them are different. A reasonable explanation is given through our research.