Synthesis, spectroscopic and structural properties of CF3SO2OCCl3

Trichloromethyl trifluoromethanesulphonate, CF₃SO₂OCCl₃, was prepared by quantitative reaction between Ag(CF₃SO₂O) and BrCCl₃. The conformational and structural properties of the gaseous molecule were studied by vibrational spectroscopy (IR (gas, liquid), Raman (liquid) and quantum chemical calculations (DFT and ab initio methods)).Theoretical and experimental vibrational results evidenced the presence of a single conformer with C₁ symmetry. This result is in agreement with the adopted geometry of covalent sulphonates. The conformational preference was studied using the total energy scheme and natural bond orbital partition scheme. Additionally, the total potential-energy has been deconvoluted using six fold decomposition in terms of a Fourier-type expansion.     

混配配合物[Zn(CF3COO)2(C7H6NS)2]的合成、晶体结构及表征

A mixed complex [Zn(CF₃COO)₂(C₇H₆NS)₂] was synthesized based on the reaction of Zn(CF₃COO)₂ and 2-aminobenzothiazol (C₇H₆NS) in methanol. The structure of the complex was characterized by elemental analysis, IR, ¹H NMR and thermal analysis. The crystal structure of the complex was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group C2/c, a=3.174 3(9) nm, b=1.010 0(3) nm, c=1.723 1(5) nm, β=118.841(4)°, V=4.839(2) nm³; D_c=1.625 g·cm^-3; Z=8; F(000)=2 368; μ=1.266 mm^-1. CCDC: 600233.     

Synthesis and structure of the silylated benzene radical anion salts [K([18]crown-6){C6H4(SiMe3)2-1,4}] and [K([18]crown-6)(THF)2][C6H2(SiMe3)4-1,2,4,5]

The crystalline compound [K([18]crown-6){C₆H₄(SiMe₃)₂-1,4}] (1) was prepared by the low-temperature reduction of the para-disilylated benzene with K/[18]crown-6 in toluene followed by recrystallisation from the same solvent. Reduction of 1,2,4,5-tetrasilylated benzene with 2(K/[18]crown-6) in toluene produced a hydrocarbon-insoluble powder identified as the dianionic derivative [K([18]crown-6)]₂[C₆H₂(SiMe₃)₄-1,2,4,5)] (2), which upon crystallisation from THF/Et₂O yielded [K([18]crown-6)(THF)₂][C₆H₂(SiMe₃)₄-1,2,4,5] (3). An X-ray diffraction study revealed that 1 comprised a contact ion pair with the crown-encapsulated K cation η⁵-connected to the planar ring of the substituted benzene radical anion, while 3 contained a well separated cation and anion.     

三维配位聚合物[C4H12N2]3[PMo12O40]的合成、结构及其电化学性质

The title compound [C4H12N2] 3 [PMo12O40] was synthesized from the hydrothermal reaction and charac-terized by IR, elemental analysis and X-ray signal crystal structural analysis. The crystal of the title complex belongs to trigonal space group R3c with a=1.788 62 nm, c=2.354 3 nm, and V=6.522 62 nm3, Z=6, R1=0.038 4, wR2=0.102 0. The compound consisted of piperazine and PMo12O403-, and the structure is extended to three dimensional framework owing to the hydrogen bond between the O atoms and N atoms. The bulk-modified carbon paste electrode (APM-CPE) using this compound as modifier shows a good electrocatalytic activity toward the oxidation of ascorbic acid(AA). CCDC: 707968.     

Arene-rhodium(I) complexes with trimethyltetrafluorobenzobarrelene. Crystal structure of [Rh(Me3TFB)(1,4-C6H4Me2)]ClO4

The preparation of arene-rhodium(I) complexes of the general formula Rh(Me₃TFB)PhBPh₃ and [Rh(Me₃TFB)(arene)]ClO₄ (Me₃TFB = trimethyltetrafluorobenzobarrelene; arene = C₆H_6?nMe_n (n = 0, 1, 2, 3, 4 or 6); C₆H_6?nX_n (X = F, n = 2 or 6; X = Cl, n = 1 or 2) are described. For arenes of the type C₆H_6?nX_n the dissociation of the coordinated arene (studied by NMR spectroscopy in deuteroacetone) is complete, but for arenes of the type C₆H_6?nMe_n it decreases with increasing methyl substitution in the arene ligand.The crystal structure of [Rh(Me₃TFB)(1,4-C₆H₄Me₂)]ClO₄ has been determined by X-ray diffraction. The compound crystallizes in the Pbca space group, with lattice periodicities of 17.7393(4), 15.7816(3) and 16.0071(3) Å. δR-analysis, for the 3953 total recorded reflections, support the refinement carried out to a final R-value of 0.062. The bonding of the arene to the rhodium is η⁶, with the ring slightly puckered to give a distorted skew conformation.     

The syntheses and mass spectra of P[CCCF3]3, As[CCCF3]3, and Sb[CCCF3]3

The syntheses of P[CCCF₃]₃, As[CC CF₃]₃, and Sb[CCCF₃]₃ are reported. The compounds are colorless and volatile, with melting points of ?20° to ?25°, 23–24°, and 55–56°C, respectively. The mass spectra show the molecular ion of each compound. The rearrangement ion [F₃CCCCCCF₂]⁺] gives the strongest peak in each spectrum.     

Structure and bonding in a series of cyano complexes: RuCp(PPh3) 2CN, [RuCp(PPh3) 2(CNH)]CF3SO3, and H-bridged [Ru2(Cp) 2(PPh3) 4CNHNC]CF3SO3

The three title cyanoruthenium complexes have been characterized by means of X-ray diffraction analysis, IR and NMR solution spectroscopies, as well as extended Hückel molecular orbital calculations examining the properties of the cyanide fragment changing with complexation and with the co-ligands Cp and PPh₃. Explanations are given for crystallographic results of the C-N bond shortening upon complexation, the supershort (2.573 Å) bond length of N(H) N in the bridged complex, as well as the Ru-C-N and C-N-H-N-C bendings. Although the crystallographically found asymmetry of coordinated Cp is not significant, the MO calculations suggest a distorted endocyclic bond-length pattern indicative of the relative importance of σ and π bonding in the metalcyclopentadienyl interactions.     

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.     

Dimethylindium hydrazides [Me2In-NH-NHR]2 (R = CMe3, C6H5)

Trimethylindium reacted with phenyl- and tert-butylhydrazine by the release of methane and the formation of the corresponding dimethylindium hydrazides (1 and 2, respectively). Both products form dimers and possess four-membered In₂N₂ heterocycles with two exocyclic N-N bonds in their molecular cores. Interestingly, one compound (1) crystallizes with centrosymmetric molecules in which the N-N bonds are located on different sides of the In₂N₂ ring (C_2h), while both N-N bonds are on the same side in 2 (C_2v). In contrast, the reaction of tri(tert-butyl)indium with tert-butylhydrazine yielded a quite unexpected product. Partial decomposition occurred, and in a low yield the adduct of tribenzylindium with the unchanged tert-butylhydrazine was isolated. In a remarkable reaction, the trialkylindium derivative did not react with the relatively acidic hydrazine, but by the release of the corresponding alkane with the solvent toluene.     

Solvothermal Synthesis, Crystal Structure Determination, and Properties of the Thioantimonate [Ph4P]2[Sb6S10]

 The reaction of elemental antimony with elemental sulfur and [Ph₄P]Br in an aqueous solution of neopentanediamine under solvothermal conditions yields yellow needles of the new thioantimonate(III) [Ph₄P]₂[Sb₆S₁₀]. The structure consists of [Ph₄P]⁺ cations and infinite one-dimensional anionic (Sb₆S₁₀ ²⁻)_n chains running along the crystallographic a axis. The chains are composed of 10-membered Sb₅S₅ rings with alternating Sb and S atoms and separated by the tetraphenylphosphonium cations. Upon heating the compound decomposes in two distinct steps, starting at about 100°C. The final product was identified by X-ray powder diffractometry as Sb₂S₃.     

一种新型多孔道配位聚合物[La(C8H6NO2)3]n的合成及晶体结构表征

A novel porous coordination polymer [La(C₈H₆NO₂)₃]_n was synthesized by hydrothermal reaction of flexible ligands 3-(3-pyridyl)acrylate and La(NO₃)₃·6H₂O. The structure was characterized by elemental analysis， IR spectroscopy and X-ray single crystal diffraction. X-ray single crystal analysis reveals the structure consists of [La(C₈H₆NO₂)₃]_n. It crystallizes in monoclinic crystal system with space group P2(1)/c. Crystallographic date: a=0. 7889(3)nm， b=2.5916(9)nm， c=1.1489(4)nm， α=90.00°， β=95.219(6)°， γ=90.00°， V=2.3393(15)nm³， Z=4， D_c=1.656g·cm^-3， μ=1.871mm^-1， F(000)=1152， R₁=0.0328， wR₂=0.0522. CCDC: 211700.     

The metathesis reactions of [SNS][SbF6] and [SN][AsF6] with Li[Al(OC(CF3)3)4] in liquid SO2

The small di- and triatomic molecules [SN]⁺ and [SNS]⁺ have shown versatile chemistries and [SNS]⁺ is an important starting reagent for many sulfur-nitrogen radicals. However, their chemistry is limited to the more polar solvents (e.g. SO₂). In this work an attempt is made to increase their solubility in less polar solvents by exchange of the usual [MF₆]⁻ (M = As, Sb) anions by the large and weakly coordinating [Al(OC(CF₃)₃)₄]⁻. As expected the metathesis reactions of [SN][AsF₆] and [SNS][SbF₆] with Li[Al(OC(CF₃)₃)₄] in liquid sulfur dioxide resulted in the formation of the insoluble Li[SbF₆], which is the driving force for these metathesis reactions. The characterization of the compounds by IR and multinuclear NMR revealed that [SNS]⁺ formed a [Al(OC(CF₃)₃)₄]⁻ salt in a clean reaction. A preliminary crystal structure of [SNS][Al(OC(CF₃)₃)₄] is presented. The solubility of [SNS][Al(OC(CF₃)₃)₄] in CH₂Cl₂ is significantly increased with respect to the corresponding [MF₆]⁻ salts, and potentially opens up new areas of [SNS]⁺ chemistry. The reaction of the more reactive [SN]⁺ with Li[Al(OC(CF₃)₃)₄] was less clear. Multinuclear NMR and IR spectra were consistent with the formation of [SN][Al(OC(CF₃)₃)₄], which also showed significant decomposition.     

Novel ammonium hexafluoroarsenate salts from reaction of (CF3)2NH,CF3N(OCF3)H,CF3N[OCF(CF3)2]H,CF3NHF and SF5NHF with the strong acid HF/ASF5.

Reactions of the fluorinated amines (CF₃)₂NH, CF₃N(OCF₃)H, CF₃N[OCF(CF₃)₂]H, CF₃NHF and SF₅NHF with the strong acid HF/AsF₅ form the corresponding ammonium salts R_f¹R_f²NH₂⁺AsF₆^? and R_fNFH₂⁺ AsF₆^? in high yield. [R_f¹=CF₃, R_f²=CF₃, CF₃O, (CF₃)₂CFO; R_f=CF₃, SF₅] The colorless crystalline solids are stable for prolonged periods at 22°C in sealed FEP containers. They have dissociation pressures at 22°C ranging from ～5 torr (R_fNFH₂⁺ AsF₆^?) to ～50 torr [CF₃N(OCF₃)H₂⁺AsF₆^?]. ¹⁹F NMR and Raman spectroscopy were used to identify the compounds.     

Electrochemical preparation of graphite intercalation compounds containing a cyclic amide, [CF2(CF2SO2)2N]

Graphite intercalation compounds (GICs) containing the cyclo-hexafluoropropane-1,3-bis(sulfonyl)amide anion, [CF₂(CF₂SO₂)₂N]⁻, are prepared for the first time. Stages 2 and 3 GICs are obtained by electrochemical oxidation of graphite in a nitromethane electrolyte. Gallery heights of 0.85-0.86 nm are determined by powder X-ray diffraction, and the intercalate anion orientation within the intercalate galleries is modeled using an energy minimized anion structure. GIC compositions are determined by thermogravimetric, fluorine and nitrogen analyses. The chemical preparation and bifluoride displacement reactions are compared with a GIC containing the linear bis(trifluoromethanesulfonyl)amide anion, [(CF₃SO₂)₂N]⁻.     

Azamacrocyclic stabilization of SbCl2: synthesis and crystal structure of [SbCl2(Me3[9]aneN3)][SbCl6] showing explicit Sb lone-pair stereochemical activity. Me3[9]aneN3 = 1,4,7-trimethyl-1,4,7-triazacyclononane

The reaction of antimony(III)chloride and antimony(V)chloride in acetonitrile in the presence of the azamacrocyclic ligand Me₃[9]aneN₃ provides the golden-yellow ionic compound [SbCl₂(Me₃[9]aneN₃][SbCl₆]. X-ray structural characterization reveals the cation as five-coordinate with Ψ-octahedral metal geometry featuring a cis-SbCl₂⁺ unit coordinated to the three donor nitrogen atoms of the ligand (fac) and a stereochemically active lone pair occupying the sixth site in a trans-position to a ring nitrogen atom.     

N-(2-吡咯甲基)-1-苯基乙亚胺·二甲基铝的合成、结构及其催化丙交酯的活性

通过席夫碱配体N-（2-吡咯甲基）-1-苯基乙亚胺与三乙基铝按物质的量之比为1：1在无氧无水的条件下反应,合成了席夫碱铝的有机金属化合物N-（2-吡咯甲基）-1-苯基乙亚胺·二甲基铝。其结构分别用核磁氢谱、碳谱,元素分析和X射线单晶衍射技术进行了表征。铝化合物在催化外消旋丙交酯开环聚合反应中表现出了中等的活性并得到了以等规聚合为主的高聚物。     

Synthesis,crystallographic data and thermostability of some metal ortho-tellurates of the type Me3TeO6 and Me2TeO6

A method of synthesis of some metal ortho-tellurates of the type Me₃TeO₆ and Me₂TeO₆ was developed. Crystallographic data (parameters of the elementary cell and the number of the formula units of these compounds) were calculated. Their picnometric density and X-ray density were determined and compared. The thermostability of these ortho-tellurates was studied.     

2,5-Dichloro-1-(ROSO2)benzene [R = C6H5, C6F5, and CH2(CF2)4H]: Synthesis, molecular structure, and solubility in supercritical CO2

Highly crystalline phenyl 2,5-dichlorobenzenesulfonate (PDBS, T_melt = 86-87 °C) and pentafluorophenyl 2,5-dichlorobenzenesulfonate (FPDBS, T_melt = 120-122 °C) were synthesized. Single-crystal X-ray molecular structure determinations show that both compounds have similar three-dimensional molecular structures; however, PDBS crystals are thin platelets and FPDBS crystals form hexagonal tube-like structures that are predominately hollow at one end. PDBS crystals exhibit offset π-stacking of the phenoxy-rings that form complete two-dimensional layers each two molecules thick. Hydrogen-bonding interactions are calculated at ∼3.2 Å between the C6-hydrogen and the sulfonyl-oxygen of a neighboring molecule. On the other hand, for FPDBS, π-stacking of the dichloro-substituted ring as well as dipole-dipole interactions of the fluorinated-phenoxy rings appears to be the predominate intermolecular interactions. Neither structure exhibits any kind of side-on interaction of the phenyl rings. PDBS and FPDBS exhibit melting point depressions of 26 and 40 °C, respectively, in the presence of supercritical CO₂. Although both sulfonates exhibit high solubility in CO₂, much lower pressures are needed to dissolve FPDBS compared to PDBS. For example, at 100 °C FPDBS dissolves at 4750 psia and PDBS dissolves at 11,000 psia. The solubility data reinforce the observation that fluorinating a compound can significantly lower the conditions needed to dissolve that compound in CO₂.     

Solubility of trans-Co2(CO)6 [3,5-bis(CF3)C6H3P(i-C3H7)2] in dense carbon dioxide

The title compound (1) was prepared by the reaction of 3,5-bis(CF₃)C₆H₃P(i-C₃H₇)₂ (L1) and Co₂(CO)₈. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to (p-CF₃C₆H₄)₃P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents.