Preparation, crystal structures, EPR and reflectance spectra of two new charge-transfer salts, [CpFeCpCH2N(CH3)3]4[XMo12O40] · nCH3CN (n = 0 for X = P or n = 1 for X = Ge)

Two new charge-transfer salts, [CpFeCpCH₂N(CH₃)₃]₄[PMo₁₂O₄₀] · CH₃CN (1) and [CpFeCpCH₂N(CH₃)₃]₄[GeMo₁₂O₄₀] (2), were synthesized by the traditional solution synthetic method and their structures were determined by single-crystal X-ray analysis. Salt 1 belongs to the triclinic space group P1, and salt 2 belongs to the triclinic space group . There exist the complex interactions of the cationic ferrocenyl donor and Keggin polyanion in the solid state. The solid state UV-Vis diffuse reflectance spectra indicate the presence of a charge-transfer band climbing from 450 nm to well beyond 900 nm for 1, a charge-transfer band from 460 to 850 nm with λ_max = 630 nm for 2.The EPR spectra of salts 1 and 2 at 77 K show a signal at g = 2.0048 and 1.9501, respectively, ascribed to the delocalization of one electron in reduced Keggin ion in salt 1 and the Mo^VI in [GeMo₁₂O₄₀]⁴⁻ is partly reduced to Mo^V owing to the charge-transfer transitions taking place between the ferrocenyl donors and the POM acceptors. The two compounds were also characterized by IR spectroscopy and cyclic voltammetry.     

Molecular structure and IR absorption spectra of perfluorinated aldehyde hydrates (n-CxF2x+1CH(OH)2, x = 1-4)

Structures and IR absorption spectra of the conformational isomers of perfluorinated aldehyde hydrates, n-C_xF_2x+1CH(OH)₂, (x = 1-4) have been calculated using density functional theory (DFT) and compared to experimental FT-IR measurements. Two absorption peaks around 3600-3700 cm⁻¹ were observed and are assigned to OH stretching modes of OH groups with, and without, intramolecular hydrogen bonding. For n-C₃F₇CH(OH)₂, two absorption bands around 900-1000 cm⁻¹ were observed in the experimental spectra, whereas only a single in-phase stretching mode of the (CF₃)(C₂F₄CH(OH)₂) and (C₃F₇)(CH(OH)₂) bonds was calculated for each conformer. The experimental spectra were well described by composite spectra of the thermal equilibrium mixture of different conformational isomers of n-C_xF_2x+1CH(OH)₂ calculated by DFT.     

Synthesis and characterisation of [AlMen{Si(SiMe3)3}3−n(thf)] (n = 1 or 2)

The crystalline compounds [AlMe_n{Si(SiMe₃)₃}_3−n(thf)] [n = 2 (1) or 1 (2)] were prepared from the lithium sisyl [Li{Si(SiMe₃)₃}(thf)₃] (A) and the appropriate methylaluminium chloride [AlCl_3−nMe_n] in thf. The X-ray structure of 1 is reported. Unlike A or a magnesium sisyl [Mg{Si(SiMe₃)₃}₂(thf)₂] (B), neither 1 nor 2 underwent an insertion reaction with an α-H-free nitrile.     

Two noncentrosymmetric complexes: [W(CO)4(bipy)] and [W(CO)4(phen)](bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) obtained through solvothermal synthesis and their optical properties

Solvothermal treatments of W(CO)₆ with 2,2′-bipyridine and 1,10-phenanthroline give [W(CO)₄(bipy)] (1) and [W(CO)₄(phen)] (2), respectively, which both crystallize in noncentrosymmetric space groups, suggesting that they meet the requirement of second harmonic generation (SHG) investigations. The preliminary experiment indicates that they are SHG active, and approximately estimated to be that of urea.     

Template-directed synthesis of macrocyclic aminopyridines: azacalix[n](2,6)pyridines (n = 3, 4)

Template-induced synthetic routes for azacalix[n](2,6)pyridines (n = 3, 4) have been elaborated. The proton and nickel ion served as the efficient template for the cyclization reactions, and the presence of the templates preferentially afforded the cyclic trimers and tetramers in moderate to good yields, respectively. The compatibility of the cyclic tetramer with nickel ion was also confirmed by X-ray crystallography.     

Separation and quantification of [RhCln(H2O)6−n] (n = 0-6) complexes, including stereoisomers, by means of ion-pair HPLC-ICP-MS

A hyphenated ion-pair (tetrabutylammonium chloride—TBACl) reversed phase (C₁₈) HPLC-ICP-MS method (High Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectroscopy) for anionic Rh(III) aqua chlorido-complexes present in an HCl matrix has been developed. Under optimum chromatographic conditions it was possible to separate and quantify cationic Rh(III) complexes (eluted as a single band), [RhCl₃(H₂O)₃], cis-[RhCl₄(H₂O)₂]⁻, trans-[RhCl₄(H₂O)₂]⁻ and [RhCl_n(H₂O)_6−n]³⁻ⁿ (n = 5, 6) species. The [RhCl_n(H₂O)_6−n]³⁻ⁿ (n = 5, 6) complex anions eluted as a single band due to the relatively fast aquation of [RhCl₆]³⁻ in a 0.1 mol L⁻¹ TBACl ionic strength mobile phase matrix. Moreover, the calculated t_1/2 of 1.3 min for [RhCl₆]³⁻ aquation at 0.1 mol kg⁻¹ HCl ionic strength is significantly lower than the reported t_1/2 of 6.3 min at 4.0 mol kg⁻¹ HClO₄ ionic strength. Ionic strength or the activity of water in this context is a key parameter that determines whether [RhCl_n(H₂O)_6−n]³⁻ⁿ (n = 5, 6) species can be chromatographically separated. In addition, aquation/anation rate constants were determined for [RhCl_n(H₂O)_6−n]³⁻ⁿ (n = 3-6) complexes at low ionic strength (0.1 mol kg⁻¹ HCl) by means of spectrophotometry and independently with the developed ion-pair HPLC-ICP-MS technique for species assignment validation. The Rh(III) samples that was equilibrated in differing HCl concentrations for 2.8 years at 298 K was analyzed with the ion-pair HPLC method. This analysis yielded a partial Rh(III) aqua chlorido-complex species distribution diagram as a function of HCl concentration. For the first time the distribution of the cis- and trans-[RhCl₄(H₂O)₂]⁻ stereoisomers have been obtained. Furthermore, it was found that relatively large amounts of ‘highly’ aquated [RhCl_n(H₂O)_6−n]³⁻ⁿ (n = 0-4) species persist in up to 2.8 mol L⁻¹ HCl and in 1.0 mol L⁻¹ HCl the abundance of the [RhCl₅(H₂O)]²⁻ species is only 8-10% of the total, far from the 70-80% as previously proposed. A 95% abundance of the [RhCl₆]³⁻ complex anion occurs only when the HCl concentration is above 6 mol L⁻¹. The detection limit for a Rh(III) species eluted from the column is below 0.147 mg L⁻¹.     

Hydrothermal synthesis, crystal structures and fluorescence properties of three novel frameworks constructed with mixed ligands of isophthalic acid (1,3-BDC) and 2,3-di-2-pyridylquinoxaline (Dpdq): [M(1,3-BDC)(Dpdq)(H2O)m] · nH2O (M = Co, Cd or Zn)

Three novel metal-organic frameworks [M(1,3-BDC)(Dpdq)(H₂O)_m] · nH₂O, (M = Co^II (1), Cd^II (2) or Zn^II (3); m = 0, 1; n = 0, 1, 2, respectively) have been obtained from hydrothermal reactions of three different metal(II) nitrates with the same mixed ligands [isophthalic acid (1,3-BDC) and 2,3-di-2-pyridylquinoxaline (Dpdq)], and structurally characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray analyses show that each pair of metal ions are bridged by various coordination modes of 1,3-BDC ligands to form left- and right-handed helical chains in 1, linear chains in 2, and double chains in 3, respectively. N-containing flexible ligand Dpdq takes a chelating coordination mode acting as terminal ligand. In the compound 1, adjacent left- and right-handed helical chains are packed through hydrogen bonds to form a two-dimensional (2-D) structure. In the compounds 2 and 3, adjacent chains are further linked by hydrogen bonds and/or π-π stacking interactions to form a three-dimensional (3-D) distorted hexagon meshes supramolecular framework for 2 and a ZnS-related three-dimensional (3-D) topology for 3, respectively. The different structures of compounds 1-3 illustrate that the influence of the metal ions in the self-assembly of polymeric coordination architectures. In addition, compounds 2 and 3 exhibit blue emission in the solid state at room temperature.     

A computational study of SbnF5n (n = 1-4): Implications for the fluoride ion affinity of nSbF5

This contributions shows with a series of ab initio MP2 and DFT (BP86 and B3-LYP) computations with large basis sets up to cc-pVQZ quality that the literature value of the standard enthalpy of depolymerization of Sb₄F_20(g) to give SbF_5(g) (+18.5 kJ mol⁻¹) [J. Fawcett, J.H. Holloway, R.D. Peacock, D.R. Russell, J. Fluorine Chem. 20 (1982) 9] is by about 50 kJ mol⁻¹ in error and that the correct value of (Sb₄F_20(g)) is +68 ± 10 kJ mol⁻¹. We assign , , and values for Sb_nF_5n with n = 2-4 and compare the results to available experimental gas phase data. Especially the MP2/TZVPP values obtained in an indirect procedure that rely on isodesmic reactions or the highly accurate compound methods G2 and CBS-Q are in excellent agreement with the experimental data, and reproduce also the fine experimental details at temperatures of 423 and 498 K. With these data and the additional calculation of [Sb_nF_5n+1]⁻ (n = 1-4), we then assessed the fluoride ion affinities (FIAs) of Sb_nF_5n(g), nSbF_5(g), nSbF_5(l) and the standard enthalpies of formation of Sb_nF_5n(g) and [Sb_nF_5n+1]⁻_(g): FIA(Sb_nF_5n(g)) = 514 (n = 1), 559 (n = 2), 572 (n = 3) and 580 (n = 4) kJ mol⁻¹; FIA(nSbF_5(g)) = 667 (n = 2), 767 (n = 3) and 855 (n = 4) kJ mol⁻¹; FIA(nSbF_5(l)) = 434 (n = 1), 506 (n = 2), 528 (n = 3) and 534 (n = 4) kJ mol⁻¹. Error bars are approximately ±10 kJ mol⁻¹. Also the related Gibbs energies were derived. Δ_fH°([Sb_nF_5n+1]⁻_(g)) = −2064 ± 18 (n = 1), −3516 ± 25 (n = 2), −4919 ± 31 (n = 3) and −6305 ± 36 (n = 4) kJ mol⁻¹.     

Synthesis, crystal structure and bioactivity of a novel 18-metallacrown-6 [Mn6(H2O)6 (anshz)6] · 10DMF

A novel macrocyclic hexanuclear manganese(III) 18-metallacrown-6 compound, [Mn₆(H₂O)₆ (anshz)₆] · 10DMF, has been prepared using a trianionic pentadentate ligand N-acetyl-5-nitrosalicylhydrazide (anshz³⁻) and characterized by X-ray diffraction (DMF = N,N-dimethylformamide). The crystal structure contains a neutral 18-membered metallacrown ring consisting of six Mn(III) and six anshz³⁻ ligands. The 18-membered metallacrown ring is formed by the succession of six structural moieties of the type [Mn(III)NN]. Due to the meridional coordination of the ligand to the Mn³⁺ ion, the ligand enforces the stereochemistry of the Mn³⁺ ions as a propeller configuration with alternating Δ/Λ forms. The disc-shaped hexanuclear ring shows at its largest diameter about 7.14 Å at entrance, about 9.76 Å at the center of the cavity, respectively. Antibacterial screening data showed that the manganese metallacrown has strong antimicrobial activity against Bacillus subtilis.     

Steric and electronic properties in bicyclic phosphines. Crystal and molecular structures of Se = Phoban-Q (Q = C2, C3Ph, Cy and Ph)

Reacting a series of the bicylic Phoban-Q (9-Q-9-phosphabicyclo[3.3.1]nonane and 9-Q-9-phosphabicyclo[4.2.1]nonane) derivatives (Q = alkyl, cyclo alkyl, aryl) with KSeCN results in the formation of the corresponding phosphine selenides. The first order phosphorus-selenium coupling constants, ¹J_P-Se, ranges from 682 to 689 Hz for the [3.3.1] isomers and from 703 to 717 Hz for the [4.2.1] isomers indicating the former to be significantly more electron rich. The crystal structures of Se = Phoban[3.3.1]-Q (Q = CH₂CH₃, C₃H₆Ph, Cy, and Ph) and Se = Phoban[4.2.1]-Q (Q = Cy and Ph) are reported and reveal PSe bond distances ranging from 2.1090(9) to 2.1245(7) Å. For Q = Cy and Ph the two isomers ([3.3.1] and [4.2.1]) co-crystallise in the same crystal enabling the determination of the molecular structures for both from the same data collection. The cone angles for all ligand derivatives were determined according to the Tolman model but by using the actual P-Se bond distances and were found to be virtually identical ranging from 165° to 175°. Changes in the Q substituent have a minor effect on the overall steric and electronic properties of the Phoban family of ligands and can be used to manipulate physical properties without changing the chemical properties significantly.     

Palladium(I) carbonyl carboxylate clusters cyclo-[Pd2(μ-CO)2(μ-OCOR)2]n (n = 2 or 3): Structure and reactivity

The interaction of palladium(+1) cluster Pd₄(μ-CO)₄(μ-OAc)₄ with saturated and unsaturated carboxylic acids was studied. It was found, that the substitution of acetates groups on others carboxylates leads to the clusters with different nuclearity. Palladium(+1) carbonyl carboxylate complexes of composition [Pd(μ-CO)(μ-OCOR)]_n, where R = CF₃, CCl₃, CH₂Cl, MeCH = CMe, Me, Prⁱ, Bu, Buⁱ, Bu^tert, n-C₅H₁₁ and n = 4 or 6 were synthesized. According to X-ray data all clusters possess cyclic planar metal cores with alternate pairs of μ-carbonyl and μ-carboxylate ligands. The presence of bulky alkyl fragments in the carboxylate ligand increases the nuclearity of the cluster compared to that of the starting palladium(+1) carbonyl acetate of composition Pd₄(μ-CO)₄(μ-OAc)₄ due, apparently, to steric hindrance.     

Alkaline earth metal poly(hydrogen fluorides) hexafluoroarsenates(V) and hexafluorophosphate(V): M2(H2F3)(HF2)2(AF6) (M = Ca, A = As; M = Sr, A = As, P)

New compounds of the type M₂(H₂F₃)(HF₂)₂(AF₆) with M = Ca, A = As and M = Sr, A = As, P) were isolated. Ca₂(H₂F₃)(HF₂)₂(AsF₆) was prepared from Ca(AsF₆)₂ with repeated additions of neutral anhydrous hydrogen fluoride (aHF). It crystallizes in a space group P4₃22 with a = 714.67(10) pm, c = 1754.8(3) pm, V = 0.8963(2) nm³ and Z = 4. Sr₂(H₂F₃)(HF₂)₂(AsF₆) was prepared at room temperature by dissolving SrF₂ in aHF acidified with AsF₅ in mole ratio SrF₂:AsF₅ = 2:1. It crystallizes in a space group P4₃22 with a = 746.00(12) pm, c = 1805.1(5) pm, V = 1.0046(4) nm³ and Z = 4. Sr₂(H₂F₃)(HF₂)₂(PF₆) was prepared from Sr(XeF₂)_n(PF₆)₂ in neutral aHF. It crystallizes in a space group P4₁22 with a = 737.0(3) pm, c = 1793.7(14) pm, V = 0.9744(9) nm³ and Z = 4. The compounds M₂(H₂F₃)(HF₂)₂(AF₆) gradually lose HF at room temperature in a dynamic vacuum or during being powdered for recording IR spectra or X-ray powder ray diffraction patterns. All compounds are isotypical with coordination of nine fluorine atoms around a metal center forming a distorted Archimedian antiprism with one face capped. This is the first example of the compounds in which H₂F₃⁻ and HF₂⁻ anions simultaneously bridge metal centers forming close packed three-dimensional network of polymeric compounds with low solubility in aHF. The HF₂⁻ anions are asymmetric with usual F?F distances of 227.3-228.5 pm. Vibrational frequency (ν₁) of HF₂⁻ is close to that in NaHF₂. The anion H₂F₃⁻ exhibits unusually small F?F?F angle of 95.1°-97.6° most probably as a consequence of close packed structure.     

A series of three-dimensional coordination polymers with general formula [{Ln(H2O)n}{Re6Te8(CN)6}] · xH2O (Ln = Eu,Gd, Tb,Dy, Ho,Er, Tm,Yb; n = 3, 4, x = 0, 2.5)

A series of new compounds containing rare earth cations (Eu to Yb) and paramagnetic cluster anion [Re₆Te₈(CN)₆]³⁻ was prepared and investigated. The X-ray structural analyses have revealed that the compounds [{Ln(H₂O)₄}{Re₆Te₈(CN)₆}] · 2.5H₂O; Ln = Eu (1), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), [{Gd(H₂O)₃}{Re₆Te₈(CN)₆}] · 2.5H₂O (2) and [{Yb(H₂O)₄}{Re₆Te₈(CN)₆}] (8) are three-dimensional polymers based on Re–CN–Ln interactions. Measurements of magnetic susceptibility for 2 and 5 showed that effective magnetic moment (at 300 K) was 8.13 μ_B for compound 2 and 10.79 μ_B for compound 5 with weak antiferromagnetic ordering appeared at low temperatures.     

(p, ρ, T) properties, and apparent molar volumes V? of ZnBr2 in methanol at T = (298.15 to 398.15) K and pressures up to p = 40 MPa

The (p, ρ, T) properties of pure methanol, the (p, ρ, T) properties and apparent molar volumes V_? of ZnBr₂ in methanol at T = (298.15 to 398.15) K and pressures up to p = 40 MPa are reported, and apparent molar volumes have been evaluated. The experimental (p, ρ, T, m) values were described by an equation of state. For the solutions the experiments were carried out at molalities m = (0.05772, 0.37852, 0.71585 and 1.95061) mol · kg⁻¹ of zinc bromide.     

Synthesis,structure and properties of [ML(NO3)2]: M = Co,Ni, Cu; L = N-(2-pyridylethyl)pyridine-2-carbaldimine

Syntheses of complexes of the type [ML(NO₃)₂], where M = Co(II), Ni(II), and Cu(II), L = N-(2-pyridylethyl)pyridine-2-carbaldimine, a tridentate ligand, are described. They were characterized by elemental analysis, spectral, magnetic, thermal studies, and X-ray crystallography. In the cobalt (1), nickel (2), and copper (3) complexes, the bivalent metal ion is coordinated by the three nitrogen atoms of the tridentate L with two pyridine-N groups occupying trans positions. Amongst the two nitrates one coordinates in a bidentate fashion while the other adopts a monodentate fashion. The X-band EPR spectra of 1, 2, and 3 in the polycrystalline state and in acetonitrile solution at 77 K are reported. Room temperature vibrating sample magnetometer data of 1, 2, and 3 afforded μ_eff values respectively of 3.928, 3.897, and 1.952 BM. The thermal stability order is 1 > 2 > 3, showing a reverse Irving-Williams trend.     

Isobutene-isoprene copolymerization initiated by [Cp∗MMe2][(n-C18H37E)B(C6F5)3] (M = Ti, Hf; E = O, S) and related compounds

The highly electrophilic borane B(C₆F₅)₃ reacts with e.g., n-octadecanol (n-C₁₈H₃₇OH) and n-octadecanethiol (n-C₁₈H₃₇SH) to form equilibrium mixtures of the reactants and their 1:1 adducts (n-C₁₈H₃₇EH)B(C₆F₅)₃ (E = O, S). The latter are acidic, and react with Cp∗MMe₃ (M = Ti, Hf) in polar and non-polar solvents to give methane and the unstable complexes [Cp∗MMe₂][(n-C₁₈H₃₇E)B(C₆F₅)₃]. The latter are very good initiators for the copolymerization of isobutene with isoprene at relatively high temperatures, giving high conversions to high molecular weight isobutene-isoprene copolymers. The weight average molecular weights are unusually high for the temperatures used, consistent with current theories of the role of weakly coordinating anions. The effects of changing the substituents on the alcohols are also investigated.     

New thallium iodates—Synthesis, characterization, and calculations of Tl(IO3)3 and Tl4(IO3)6, [Tl3Tl(IO3)6]

Two new thallium iodates have been synthesized, Tl(IO₃)₃ and Tl₄(IO₃)₆ [Tl⁺₃Tl³⁺(IO₃)₆], and characterized by single-crystal X-ray diffraction. Both materials were synthesized as phase-pure compounds through hydrothermal techniques using Tl₂CO₃ and HIO₃ as reagents. The materials crystallize in space groups R-3 (Tl(IO₃)₃) and P-1 (Tl₄(IO₃)₆). Although lone-pairs are observed for both I⁵⁺ and Tl⁺, electronic structure calculations indicate the lone-pair on I⁵⁺ is stereo-active, whereas the lone-pair on Tl⁺ is inert.