Crystal growth, characterization and physical properties of PrNiSb3, NdNiSb3 and SmNiSb3

The crystal structures of three new intermetallic ternary compounds in the LnNiSb₃ (Ln=Pr, Nd and Sm) family have been characterized by single crystal X-ray diffraction. PrNiSb₃, NdNiSb₃ and SmNiSb₃ all crystallize in an orthorhombic space group, Pbcm (No. 57), Z=12, with , , , and ; , , , and ; and , , , and , for Ln=Pr, Nd and Sm, respectively. These compounds consist of rare-earth atoms located above and below layers of nearly square, buckled Sb nets, along with layers of highly distorted edge- and face-sharing NiSb₆ octahedra. Resistivity data indicate metallic behavior for all three compounds. Magnetization measurements show antiferromagnetic behavior with (PrNiSb₃), 4.6 K (NdNiSb₃), and 2.9 K (SmNiSb₃). Effective moments of 3.62 μ_B, 3.90 μ_B and 0.80 μ_B are found for PrNiSb₃, NdNiSb₃ and SmNiSb₃, respectively, and are consistent with Pr³⁺ (f ²), Nd³⁺ (f ³), and Sm³⁺ (f ⁴).     

Crystal growth, transport, and magnetic properties of Ln3Co4Sn13 (Ln=La, Ce) with a perovskite-like structure

Ln₃Co₄Sn₁₃ (Ln=La, Ce) have been synthesized by flux growth and characterized by single crystal X-ray diffraction. These compounds adopt the Yb₃Rh₄Sn₁₃-type structure and crystallize in the cubic space group (No. 223) with Z=2. Lattice parameters at 298 K are , , and , for the La and Ce analogues, respectively. The crystal structure consists of an Sn-centered icosahedron at the origin of the unit cell, which shares faces with eight Co trigonal prisms and 12 Ln-centered cuboctahedra. Magnetization data at 0.1 T show paramagnetic behavior down to 1.8 K for Ce₃Co₄Sn₁₃, with per Ce³⁺, while conventional type II superconductivity appears below 2.85 K in the La compound. Electrical resistivity and specific heat data for the La compound show a corresponding sharp superconducting transition at T_c∼2.85 K. The entropy and resistivity data for Ce₃Co₄Sn₁₃ show the existence of the Kondo effect with a complicated semiconducting-like behavior in the resistivity data. In addition, a large enhanced specific heat coefficient at low T with a low magnetic transition temperature suggests a heavy-fermionic character for the Ce compound. Herein, the structure and physical properties of Ln₃Co₄Sn₁₃ (Ln=La, Ce) are discussed.     

Magnetic and transport properties of RCr0.3Ge2 (R=Tb, Dy, Ho and Er) compounds

The magnetic and transport properties of ternary rare-earth chromium germanides RCr_0.3Ge₂ (R=Y and Tb-Er) have been determined. X-ray and neutron diffraction studies indicate that these compounds have the CeNiSi₂-type structure (space group Cmcm) [1]. Magnetic measurements reveal the antiferromagnetic ordering below T_N equal to 18.5 K (R=Tb), 11.8 K (Dy), 5.8 K (Ho) and 3.4 K (Er). From the neutron diffraction data the magnetic structures have been determined. For TbCr_0.3Ge₂ and DyCr_0.3Ge₂ at low temperatures the magnetic ordering can be described by two vectors k₁=(,0,0) and k₂=(,0,), and k₁′=(,0,0) and k₂′=(,0,), respectively. In HoCr_0.3Ge₂ and ErCr_0.3Ge₂ the ordering can be described by one propagation vector equal to (,,0) and (0,0,0.4187(2)), respectively. In DyCr_0.3Ge₂ some change in the magnetic ordering is observed at T_t=5.1 K. In temperature range from T_t to T_N the magnetic ordering is given by one propagation vector k=(,0,0). YCr_0.3Ge₂ is a Pauli paramagnet down to 1.72 K which suggests that in the entire RCr_0.3Ge₂ series the Cr atoms do not carry magnetic moments. All compounds studied exhibit metallic character of the electrical conductivity. The temperature dependencies of the lattice parameters reveal strong magnetostriction effect at the respective Nèel temperatures.     

Syntheses and crystal structures of two new cationic 3,5-dimethylpyrazole derivatives containing organoiron mixed-sandwiches as substituent groups

Organometallic hydrazines formulated as , react with 2,4-pentanedione in acetonitrile to afford 3,5-dimethylpyrazole derivatives , respectively, that contain the organoiron mixed-sandwich moieties. The new complexes have been fully characterized by elemental analysis and IR, UV-vis and ¹H and ¹³C NMR spectroscopies and authenticated by single crystal X-ray diffraction analysis. Complexes crystallize in the space group P2₁/n.     

PbI4Cu2(PPh3)4: A heterometallic iodide with unusual cis-divacant octahedral coordination sphere for lead: Synthesis, structure, red-infrared fluorescence and theoretical studies

A new heterometallic iodide, PbI₄Cu₂(PPh₃)₄, was synthesized by reactions of PbI₂, CuI and triphenylphosphine (PPh₃) in DMF solution. The single-crystal X-ray diffraction analyses show that Pb(II) center adopts an unusual cis-divacant octahedral geometry. Crystal data: triclinic, space group , , , , α=106.623(4)°, β=103.478(6)°, γ=93.574(5)°, and Z=2. Density function theory (DFT) calculations and fragment orbital interaction analyses reveal the presence of a three-center four-electron (3c-4e) hypervalent bonding about lead; and the formation of the unusual cis-divacant [PbI₄]²⁻ octahedron is energetically favorable. The title yellow compound has an optical bandgap of 2.69 eV and shows remarkable red-infrared fluorescence emission at 732 nm with lifetime of 24 μs which is assigned as an iodine 5p-lead 6s to PPh₃-lead 6p charge transfer (XM-LM-CT).     

Synthesis, crystal structure, spectrum properties, and electronic structure of a novel non-centrosymmetric borate, BiCd3(AlO)3(BO3)4

A novel non-centrosymmetric borate, BiCd₃(AlO)₃(BO₃)₄, has been prepared by solid state reaction methods below 750 °C. Single-crystal XRD analysis showed that it crystallizes in the hexagonal group P6₃ with a=10.3919(15) Å, c=5.7215(11) Å, Z=2. In its structure, AlO₆ octahedra share edges to form 1D chains that are bridged by BO₃ groups through sharing O atoms to form the 3D framework. The 3D framework affords two kinds of channels that are occupied by Bi³⁺/Cd²⁺ atoms only or by Bi³⁺/Cd²⁺ atoms together with BO₃ groups. The IR spectrum further confirmed the presence of BO₃ groups. Second-harmonic-generation measurements displayed a response of about 0.5×KDP (KH₂PO₄). UV-vis diffuse reflectance spectrum showed a band gap of about 3.19 eV. Solid-state fluorescence spectrum exhibited the maximum emission peak at around 390.6 nm. Band structure calculations indicated that it is an indirect semiconductor.     

Synthesis, structure, and bridge-terminal alkyl exchange kinetics of pyrazolate-bridged dialuminum complexes containing bridging n-alkyl groups

Treatment of triethylaluminum with 3,5-diphenylpyrazole in a 2:1 stoichiometry afforded the ethyl-bridged complex Et₂Al(μ-Ph₂pz)(μ-Et)AlEt₂ (79%) as a colorless crystalline solid. Treatment of tri-n-propylaluminum with 3,5-di-tert-butylpyrazole in a 2:1 stoichiometry afforded the n-propyl-bridged complex (nPr)₂Al(μ-tBu₂pz)(μ-nPr)Al(nPr)₂ (63%) and the dimeric complex [(nPr)₂Al(μ-tBu₂pz)]₂ (3%), respectively, as colorless crystalline solids. Treatment of tri-n-propylaluminum (1 equiv.) or triisobutylaluminum (1 or 2 equiv.) with 3,5-di-tert-butylpyrazole afforded exclusively the dimeric complexes [(nPr)₂Al(μ-tBu₂pz)]₂ (68%) or [(iBu)₂Al(μ-tBu₂pz)]₂ (96%), respectively, as colorless crystalline solids. The solid state structures of Et₂Al(μ-Ph₂pz)(μ-Et)AlEt₂ and (nPr)₂Al(μ-tBu₂pz)(μ-nPr)Al(nPr)₂ consist of 3,5-disubstituted pyrazolato ligands with a di-n-alkylalumino group bonded to each nitrogen atom. An ethyl or n-propyl group acts as a bridge between the two aluminum atoms. The kinetics of the bridge-terminal exchange was determined for the bridging n-alkyl complexes by ¹³C NMR spectroscopy, and afforded ΔH^‡ = 1.5 ± 0.1 kcal/mol, ΔS^‡ = −46.8 ± 39.0 cal/K mol, and for Et₂Al(μ-Ph₂pz)(μ-Et)AlEt₂ and ΔH^‡ = 1.7 ± 0.1 kcal/mol, ΔS^‡ = −46.6 ± 43.4 cal/K mol, and for (nPr)₂Al(μ-tBu₂pz)(μ-nPr)Al(nPr)₂. The negative values of ΔS^‡ imply ordered transition states relative to the ground states, and rotation along the N-AlR₃ vector without aluminum-nitrogen bond cleavage is proposed.     

Syntheses, characterization and sensitized lanthanide luminescence of heteronuclear Pt-Ln (Ln = Eu, Nd, Yb) complexes with 2,2′-bipyridyl ethynyl ligands

Reaction of [Pt()Cl]⁺ ( = 4,4′,4′′-tri-tert-butyl-2,2′:6′,2′′-terpyridine) with 5-ethynyl-2,2′-bipyridine (HCCbpy) or 5,5′-bis(trimethylsilylethynyl)-2,2′-bipyridine (Me₃SiCCbpyCCSiMe₃) in the presence of cuprous iodide gives [Pt(^tBu₃tpy)(CCbpy)]⁺ (1) or [{Pt()}₂(CCbpyCC)]²⁺ (2) through Pt-acetylide σ-coordination, respectively. Incorporating 1 or 2 with Ln(hfac)₃(H₂O)₂ through 2,2′-bipyridyl chelating the Ln^III (Ln = Nd, Eu, and Yb) centers induces formation of a series of [Pt()(CCbpy){Ln(hfac)₃}]⁺ (PtLn) or [{Pt()}₂(CCbpyCC){Ln(hfac)₃}]²⁺ (Pt₂Ln) complexes, respectively. The structures of binuclear platinum(II) complex 2(PF₆)₂ and heterobinuclear PtNd complex 3(CF₃COO) were determined by single crystal X-ray diffraction. Both 1 and 2 exhibit typical low-energy absorption bands in near UV-Vis region, ascribed to dπ(Pt) → π^∗() MLCT and π(CCbpy/CCbpyCC) → π^∗() LLCT transitions. Upon formation of the PtLn or PtLn₂ complexes, the low-energy absorption bands are obviously blue-shifted (15-20 nm) compared with those in the Pt^II precursor 1 or 2. With excitation at 350 nm < λ < 550 nm which is the absorption region of MLCT and LLCT transitions, sensitized luminescence that is characteristic of the corresponding lanthanide(III) ions occurs in both PtLn and Pt₂Ln complexes. In contrast, Pt-based luminescence from the MLCT and LLCT states are mostly quenched in these Pt-Ln heteronuclear complexes, revealing that quite effective Pt → Ln energy transfer is operating from the Pt()(acetylide) chromophore to the lanthanide(III) centers.     

Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS3], Pr[BS3], and Nd[BS3]

The orthothioborates Ce[BS₃], Pr[BS₃] and Nd[BS₃] were prepared from mixtures of the rare earth (RE) metals together with amorphous boron and sulfur summing up to the compositions CeB₃S₆, PrB₅S₉ and NdB₃S₆. The following preparation routes were used: solid state reactions with maximum temperatures of 1323 K and high-pressure high-temperature syntheses at 1173 K and 3 GPa. Pr[BS₃] and Nd[BS₃] were also obtained from rare earth chlorides RECl₃ and sodium thioborate Na₂B₂S₅ by metathesis type reactions at maximum temperatures of 1073 K. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The thioborates are isotypic and crystallize in the orthorhombic spacegroup Pna2₁ (No. 33; Z=4; Ce: , , ; Pr: , , ; Nd: , , ) . The crystal structures contain isolated [BS₃]^3‐ groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of undulated kagome nets, which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species.     

Coordination of N-methylpyrrolidone to iron(II)

The use of NMP (N-methylpyrrolidone) as a cosolvent has been shown to improve the yield of iron-catalyzed cross-coupling reactions, but surprisingly there are no iron complexes of NMP in the literature. This paper reports two novel NMP complexes of iron(II): Fe₃Cl₆(NMP)₈ and L^tBuFe(NMP)Cl (L^tBu = bulky β-diketiminate ligand). The X-ray crystal structure of Fe₃Cl₆(NMP)₈ shows an octahedral cation and two tetrahedral FeCl₃(NMP)⁻ anions. ¹H NMR spectra show that the NMP ligands are labile, exchanging rapidly on the NMR time scale. The β-diketiminate complex has a trigonal pyramidal geometry with the NMP in an axial position. The use of NMP improves the yield of the catalytic cross-coupling of methyl 4-chlorobenzoate and 1-hexylmagnesium bromide using these and other iron complexes as precatalysts.     

A new fluorogenic calix[4]arene N-dansylcarboxamide in the cone conformation for selective optical recognition of mercury(II)

A novel fluorogenic calix[4]arene dansylcarboxamide in the cone conformation has been synthesized as the disodium salt and employed in optical recognition of mercury(II). In extraction from aqueous solutions with high content of competing Na⁺ (C_Na+ ∼0.1 M; pH 5.0, acetate buffer) into CHCl₃, the fluoroionophore allowed for detection of 8.0 × 10⁻⁷ M Hg²⁺ (1:1 complex; ) with high selectivity over many other relevant metal ions.     

An open-framework three-dimensional indium oxalate: [In(OH)(C2O4)(H2O)]3·H2O

By hydrothermal reaction of In₂O₃ with H₂C₂O₄·2H₂O in the presence of H₃BO₃ at 155 °C, an open-framework three-dimensional indium oxalate of formula [In(OH)(C₂O₄)(H₂O)]₃·H₂O (1) has been obtained. The compound crystallizes in the trigonal system, space group R3c with , , , Z=6, R₁=0.0352 at 298 K. The small pores in 1 are filled with water molecules. It loses its filled water at about 180 °C without the change of structure, then the bounded water at 260 °C, and completely decompounds at 324 °C. The residue is confirmed to be In₂O₃.     

Synthesis, crystal structure and optical properties of BiMgVO5

The new vanadate BiMgVO₅ has been prepared and its structure has been determined by single crystal X-ray diffraction: space group P2₁/n, , , , β=107.38(5)°, wR₂=0.0447, R=0.0255. The structure consists of [Mg₂O₁₀] and [Bi₂O₁₀] dimers sharing their corners with [VO₄] tetrahedra. The ranges of bond lengths are 2.129-2.814 Å for Bi-O; 2.035-2.167 Å for Mg-O and 1.684-1.745 Å for V-O. V-O bond lengths determined from Raman band wavenumbers are between 1.679 and 1.747 Å. An emission band overlapping the entire visible region with a maximum around 650 nm is observed.     

Synthesis, structural and spectroscopic properties of a new Schiff base ligand N,N′-bis(trifluoromethylbenzylidene)ethylenediamine

The Schiff base compound, N,N′-bis(trifluoromethylbenzylidene)ethylenediamine (C₁₈H₁₄F₆N₂) (1), CF₃C₆H₄CHNCH₂CH₂NCHC₆H₄CF₃ has been synthesized by adding a solution of ethylenediammine (en), 0.1 mmol in chloroform to 4-(trifluoromethyl)-benzaldehyde, CF₃C₆H₄CHO (0.2 mmol) and the product was crystallized in ethanol with the mp, 109.2 °C and 75% yield. The crystal structure was investigated by a single-crystal X-ray diffraction study at 150 K. The compound crystallizes in monoclinic space group, P2₁/c with a = 9.295(3), b = 5.976(5), c = 15.204(9) Å and α = 90°, β = 96.56(5)° and γ = 90°. The crystal structure is stabilized by intermolecular CH · · · F hydrogen bonds. The asymmetric unit contains only one-half of the molecule related to the center of symmetry coinciding with C(1)-C(1′) and as a whole, the title molecule is in the staggered conformation. The phenyl rings and the CN imine bonds are co-planar. The infrared spectrum showed a sharp peak at 1640 cm⁻¹ which is typical of the conjugated CN stretching and strong peaks at 800-1400 cm⁻¹ regions are due to the C-C and C-H stretching modes. Electronic absorption spectra exhibits strong absorption in the UV region (240 nm wavelength) which have been ascribed to , and electronic transitions. The ¹H NMR spectra showed three distinct peaks at 2.5, 7.8 and 8.5 ppm which are assigned based on the splitting of resonance signals and are clearly confirmed by the X-ray molecular structure. The aromatic protons appear at about 7.8 ppm and the imine protons at 8.5 ppm. The sharp singlet at about 3.95 ppm is assigned to the CH₂-CH₂ protons. Mass spectra of the titled compound showed the molecular ion peak at m/e 372 (M⁺), and fragments at m/e 353 (M-F), 342 (M-2F), 200 (M-CF₃C₆H₄CHN), 186 (M-CF₃C₆H₄CHNCH₂).     

Ruthenium (II) complexes of the chelating phosphine borane H2ClB · dppm

Reaction of H₂ClB · PPh₂CH₂PPh₂ (H₂ClB · dppm) with results in displacement of all three acetonitrile ligands and the formation of (1), which has been characterised crystallographically. Reaction with carbon monoxide results in a change from η² to η¹ of the borane ligand to afford (2). Compound 1 undergoes H/D exchange under a D₂ atmosphere to afford , while 2 does not.     

Oxidative addition to main group versus transition metals: Insights from the Activation Strain model

We have studied the oxidative addition of the methane C-H and chloromethane C-Cl bonds to a number of main group (Be, Mg and Ca) and transition metals (Pd, Zn and Cd), using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. The purpose is to better understand what causes the characteristic differences in reactivity between main group and transition metals towards oxidative addition. Thus, we have analyzed our model reactions using the Activation Strain model in which the activation energy ΔE^≠ is decomposed into the activation strain of and the stabilizing TS interaction between the reactants in the activated complex: . Activation of the C-H bond goes with higher barriers than activation of the C-Cl bond because the higher bond strength of the former translates into a higher activation strain . The barriers for bond activation increase along Pd < Be, Ca < Mg < Zn, Cd. This can be straightforwardly understood through the TS-interaction , that is, in terms of the bonding capabilities of the metals. Pd yields the lowest barriers because it achieves the most stabilizing . This is the result of the small HOMO-LUMO gap between its occupied 4d and unfilled 5s AOs, which makes Pd both a good electron donor and acceptor. Zn and Cd yield the highest barriers because the large HOMO-LUMO gap between the occupied valence ns and unfilled valence np AOs makes them both poor donors and poor acceptors of electronic charge.