Quantum-chemical study of organoxenon molecules Xe(CF<Subscript>3</Subscript>)<Subscript>2</Subscript> and FXeCF<Subscript>3</Subscript>

Charges on the atoms and structural parameters of the Xe(CF₃)₂, FXeCF₃, and XeF₂ molecules were calculated by the MP2(full)/MIDI(d₆)&6-311G(d ₆) quantum-chemical methods. The calculated energy of Xe(CF₃)₂ is greater by 113 kcal/mol than the overall energy of C₂F₆ and Xe, and the energy of FXeCF₃ is greater by 108 kcal/mol than the overall energy of CF₄ and Xe, the barrier to the decomposition being estimated at 40 kcal/mol. Both Xe(CF₃)₂ and FXeCF₃ molecules are stable with respect to spontaneous decomposition with elimination of difluorocarbene.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1808–1810.Original Russian Text Copyright © 2004 by Semenov, Sigolaev.     

129Xe-Kernresonanzuntersuchungen von Xenonverbindungen. II. Xenon(II)-Derivate

¹²⁹-Xe-NMR Spectra of Xenon Compounds. II Xenon (II) Compounds The ¹²⁹Xe NMR Spectra of Xe(OSeF₅)₂, Xe(OTeF₅)₂, FXe–OSeF₅, FXe–OTeF₅, and F₅SeO–Xe–OTeF₅ have been measured and discussed. The mixed compounds FXe–OSeF₅, FXe–OSeF₅, FXe–OTeF₅, and F₅SeO–Xe–OTeF₅ exist only in equilibrium with the derivatives Xe(OSeF₅)₂, Xe(OTeF₅)₂ and XeF₂. Coupling of ¹²⁹Xe is observed with the fluorine directly bonded at the Xenon atom, with the equatorial fluorine atoms on selenium and tellurium. and with the tellurium isotop ¹²⁵Te.     

Study on synthesis of lanthanide chelates of fluorochloroalkyl β-diketones useful as shift reagents

Several lanthanide chelates of the fluorochloroalkyl β-diketones Ln(CF₂ClCOCHCOR)₃ ·nH₂O were prepared (2, Ln=Eu; 2a, R=C(CH₃)₃, n=0; 2b, R=C₆F₅, n=0; 2c, R=CF₂Cl, n=2. 3, Ln=Pr; 3a, R=C (CH₃)₃, n=0; 3b, R=C₆F₅, n=l; 3c, R=CF₂Cl, n=2. 4, Ln=La, R=C₆H₅, n=0) and the NMR shift data of compounds 2 and 3 had been determined using alcohols, ether, ketones and amine as substrates. With alcohol, ether and ketone, compounds 2 induces shifts similar to that induced by Eu (fod)₃. However due to the high solubility of the chelates in non-polar organic solvents such as CHCl₃ and CCl₄ and the absence of ¹H signal from compounds 2b and 2c, their application as a series of new ¹H NMR shift reagents seems promising.     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. IV. Darstellung und Eigenschaften neuer N-silylierter Diphosphazene

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. IV. Preparation and Properties of New N-silylated Diphosphazenes Phosphazeno-phosphanes, R₃P = N? P(OR′) ₂ (R = CH₃, N(CH₃)₂; R′ = CH₂? CF₃) react with trimethylazido silane to give N-silylated diphosphazenes, R₃P = N? P(OR′)₂ = N? Si(CH₃)₃ compounds decompose by atmospherical air to phosphazeno-phosphonamidic acid esters, R₃ P?N? P(O)(O? CH₂? CF₃)(NH₂). Thermolysis of diphosphazene R₃P = N? P(OR′) ₂ = N? Si(CH₃)₃ (R = CH₃, R′ = CH₂? CF₃) produces phosphazenyl-phosphazenes [N?P(N?P(CH₃)₃)OR′] _n. The compounds are characterized by elementary analysis, IR-, ¹H_-, ²⁹Si-, ³¹P-n.m.r., and mass spectroscopy.     

A Design Strategy for Single‐Stranded Helicates using Pyridine‐Hydrazone Ligands and PbII

The reactions of py‐hz ligands ( L1–L5 ) with Pb(CF₃SO₃)₂?H₂O resulted in some rare examples of discrete single‐stranded helical Pb^II complexes. L1 and L2 formed non‐helical mononuclear complexes [Pb L1 (CF₃SO₃)₂]?CHCl₃ and Pb L2 (CF₃SO₃)₂][Pb L2 CF₃SO₃]CF₃SO₃?CH₃CN, which reflected the high coordination number and effective saturation of Pb^II by the ligands. The reaction of L3 with Pb^II resulted in a dinuclear meso‐helicate [Pb₂ L3 (CF₃SO₃)₂Br]CF₃SO₃?CH₃CN with a stereochemically‐active lone pair on Pb^II. L4 directed single‐stranded helicates with Pb^II, including [Pb₂ L4 (CF₃SO₃)₃]CF₃SO₃?CH₃CN and [Pb₂ L4 CF₃SO₃(CH₃OH)₂](CF₃SO₃)₃?2 CH₃OH?2 H₂O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with Pb^II, including a trinuclear Pb^II complex [Pb₃ L5 (CF₃SO₃)₅]CF₃SO₃?3CH₃CN?Et₂O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with Pb^II.     

The reaction of XeF+MF6− (M = As,Sb) with sulfuranes; preparation of CF3(O)F2+SbF6− and (CF3)2SOXeF+SbF6−

CF₃S(O)F, (CF₃)₂SO, CF₃SF₃, (CF₃)₂SF₂, and SF₄ react in different manner with XeF⁺MF₆^? (M?As, Sb). An oxidative fluorination is observed by CF₃S(O)F forming the persulfonium salt CF₃S(O)F₂⁺SbF₆^?, whereas by (CF₃)₂SO a simple addition product containing xenon can be isolated in form of the sulfonium salt (CF₃)₂SOXeF⁺SbF₆^?. On the contrary, the Lewis-acidic character of the XeF⁺-cation predominates against (CF₃)_nSF_4?n (n = 0 ? 2) leading to the corresponding fluorosulfonium salts (CF₃)_nSF_3?n ⁺MF₆^? (M?As, Sb) and XeF₂.     

Chiral Fluorinated α‐Sulfonyl Carbanions: Enantioselective Synthesis and Electrophilic Capture,Racemization Dynamics,and Structure

Enantiomerically pure triflones R¹CH(R²)SO₂CF₃ have been synthesized starting from the corresponding chiral alcohols via thiols and trifluoromethylsulfanes. Key steps of the syntheses of the sulfanes are the photochemical trifluoromethylation of the thiols with CF₃Hal (Hal=halide) or substitution of alkoxyphosphinediamines with CF₃SSCF₃. The deprotonation of RCH(Me)SO₂CF₃ (R=CH₂Ph, iHex) with nBuLi with the formation of salts [RC(Me)? SO₂CF₃]Li and their electrophilic capture both occurred with high enantioselectivities. Displacement of the SO₂CF₃ group of (S)‐MeOCH₂C(Me)(CH₂Ph)SO₂CF₃ (95 % ee) by an ethyl group through the reaction with AlEt₃ gave alkane MeOCH₂C(Me)(CH₂Ph)Et of 96 % ee. Racemization of salts [R¹C(R²)SO₂CF₃]Li follows first‐order kinetics and is mainly an enthalpic process with small negative activation entropy as revealed by polarimetry and dynamic NMR (DNMR) spectroscopy. This is in accordance with a C_α? S bond rotation as the rate‐determining step. Lithium α‐(S)‐trifluoromethyl‐ and α‐(S)‐nonafluorobutylsulfonyl carbanion salts have a much higher racemization barrier than the corresponding α‐(S)‐tert‐butylsulfonyl carbanion salts. Whereas [PhCH₂C(Me)SO₂tBu]Li/DMPU (DMPU = dimethylpropylurea) has a half‐life of racemization at ?105 °C of 2.4 h, that of [PhCH₂C(Me)SO₂CF₃]Li at ?78 °C is 30 d. DNMR spectroscopy of amides (PhCH₂)₂NSO₂CF₃ and (PhCH₂)N(Ph)SO₂CF₃ gave N? S rotational barriers that seem to be distinctly higher than those of nonfluorinated sulfonamides. NMR spectroscopy of [PhCH₂C(Ph)SO₂R]M (M=Li, K, NBu₄; R=CF₃, tBu) shows for both salts a confinement of the negative charge mainly to the C_α atom and a significant benzylic stabilization that is weaker in the trifluoromethylsulfonyl carbanion. According to crystal structure analyses, the carbanions of salts {[PhCH₂C(Ph)SO₂CF₃]Li? L }₂ ( L =2 THF, tetramethylethylenediamine (TMEDA)) and [PhCH₂C(Ph)SO₂CF₃]NBu₄ have the typical chiral C_α? S conformation of α‐sulfonyl carbanions, planar C_α atoms, and short C_α? S bonds. Ab initio calculations of [MeC(Ph)SO₂tBu]^? and [MeC(Ph)SO₂CF₃]^? showed for the fluorinated carbanion stronger n_C→σ* and n_O→σ* interactions and a weaker benzylic stabilization. According to natural bond orbital (NBO) calculations of [R¹C(R²)SO₂R]^? (R=tBu, CF₃) the n_C→σ*_{S? R} interaction is much stronger for R=CF₃. Ab initio calculations gave for [MeC(Ph)SO₂tBu]Li ? 2 Me₂O an O,Li,C_α contact ion pair (CIP) and for [MeC(Ph)SO₂CF₃]Li ? 2 Me₂O an O,Li,O CIP. According to cryoscopy, [PhCH₂C(Ph)SO₂CF₃]Li, [iHexC(Me)SO₂CF₃]Li, and [PhCH₂C(Ph)SO₂CF₃]NBu₄ predominantly form monomers in tetrahydrofuran (THF) at ?108 °C. The NMR spectroscopic data of salts [R¹(R²)SO₂R³]Li (R³=tBu, CF₃) indicate that the dominating monomeric CIPs are devoid of C_α? Li bonds.     

Fluorinated phosphorus compounds: Part 9. The reactions of bis(fluoroalkyl) phosphorochloridates with oxygen nucleophiles

Twenty nine bis(fluoroalkyl) phosphates (R_FO)₂P(O)OR were prepared in 18-75% yield by treating phosphorochloridates (R_FO)₂P(O)Cl, where R_F was HCF₂CH₂, HCF₂CF₂CH₂, H(CF₂)₄CH₂, C₂F₅CH₂, C₃F₇CH₂, (CF₃)₂CH, (FCH₂)₂CH and (CH₃)₂CF₃C with methanol, ethanol, propanol and isopropanol in diethyl ether in the presence of triethylamine. The bulky chloridate [(CH₃)₂CF₃CO]₂P(O)Cl reacted with methanol, ethanol and propanol, but not with isopropanol - even on heating in the presence of the catalyst 4-dimethylaminopyridine - due to steric hindrance at phosphorus. The relative reactivities of three of the chloridates decreased in the order [(CF₃)₂CHO]₂P(O)Cl > [(FCH₂)₂CHO]₂P(O)Cl > [(CH₃)₂CF₃CO]₂P(O)Cl. Also described is the synthesis of phosphates (CF₃CH₂O)₂P(O)OCH₂R, where R = CH₂Br, CH₂Cl, CH₂F and CHF₂, and diphosphates [H(CF₂)_nCH₂O]₂P(O)OCH₂(CF₂)₂CH₂OP(O)[OCH₂(CF₂)_nH]₂, where n = 1, 2 and 4.     

Dimethyl-N-Halogenamine,ihre Ammoniumsalze und Bortrihalogenid-Addukte

Dimethyl-N-Halogenoamine, their Ammonium Salts and Borontrihalide Adducts The preparation and vibrational spectra of (CH₃)₂NHCl⁺X^? (X^? = CF₃SO₃^? I , SO₃F^? II , SO₃Cl^? III , BCl₄^? IV ), and (CH₃)₂NHBr⁺CF₃SO₃^? V as well as the adducts (CH₃)₂NCl · S (S = BF₃ VI , BCl₃ VII , BBr₃ VIII ) and (CH₃)₂NBr · BF₃ IX are reported. The crystal structure of VII has been determined from three-dimensional diffractometer data at ?100°C. The Cl atom and one methyl group in the dimethyl-N-chloroamino group show disorder. The structural data are: B? Cl 183(2) pm, B? N 167(3) pm, N? C 152(3) pm (distances to disordered positions are not included).     

A Widely Applicable Synthetic Approach to Alk‐1‐yn‐1‐yl(polyfluoroorganyl)‐iodonium Salts [(RC≡C)(R′)I][BF4]

The reaction of alkynyldifluoroboranes RC≡CBF₂ (R = (CH₃)₃C, CF₃, (CF₃)₂CF) with organyliodine difluoride R′IF₂ bearing electron‐withdrawing polyfluoroorganyl groups R′ = C₆F₅, (CF₃)₂CFCF=CF, C₄F₉, and CF₃CH₂ leads to the corresponding alkynyl(organyl)iodonium salts [(RC≡C)(R′)I][BF₄]. This approach uses a widely applicable method as demonstrated for a representative series of polyfluorinated aryl‐, alkenyl‐, and alkyliodine difluorides. Generally, these syntheses proceed with good yields and deliver pure iodonium salts. The distinct electrophilic nature of their [(RC≡C)(R′)I]⁺ cations is deduced from multinuclear magnetic resonance data. Within the series of new iodonium salts [CF₃C≡C(C₄F₉)I][BF₄] is an intrinsic unstable one and decomposed forming CF₃C≡CI and C₄F₁₀.     

Mono and Bisphosphonates from Perfluoro Olefins and Polyfunctional Fluoro Ketones. Syntheses,Molecular Structure and Derivatives

Perfluoroalkenyl phosphonates were formed along with Me₃SiF using CF₃CF=CF₂, CF₃CH=CF₂, F₅SCF=CF₂ or F₅SCH=CF₂ and silylated phosphites, (R¹O)₂POSiMe₃ (R¹=Et, SiMe₃). This straightforward method could be extended to perfluorobutadienes CF₂=C(R^F)C(R^F)=CF₂ (R^F F=F, CF₃). The formation of CF₃C(=O)P(=O)(OSiMe₃)₂ and further reactions to yield bisphosphonates will be described. Acetylphosphonates, R²C(=O)P(=O)(OSiMe₃)₂ (R²=CH₃, CF₃) reacted with the ketimine, CH₃C(=NiPr)Ph to give α-hydroxy-γ-imino phosphonates. Trifluoroacetylphenol and 2,6-bis(trifluoracetyl)-4-methyl-phenol have been proven to be versatile precursors for α-and γ-hydroxy phosphonates. Intermediates in these reactions were found to be cyclic λ⁵σ⁵P species.     

Preparation and characterization of acrylates and polyacrylates having variable fluorine contents and distributions

Five acrylic esters having different fluorine contents and distributions in their side-groups (i.e., CH₂=CHC(O)OR, where R = ? C(CH₃)₂C₆F₄H, ? C(CH₃)₂C₆F₅, ? C(CF₃)₂C₆F₅, ? C(CF₃)₂C₆H₅, and ? C(CH₃)₂C₆H₅) have been prepared from the reactions of the lithium salts of their corresponding alcohols with acryloyl chloride. These monomers are polymerized under identical conditions by the radical initiator AIBN and five polyacrylates were prepared having the structure of ? [ ? CH₂CHC(O)OR? ]_n? . These addition polymers were compared and fully characterized by GPC, VPO, DSC, TGA, NMR, IR, and UV-visible spectroscopies, and they showed potential for practical applications. Significant differences in their thermal stabilities were found with respect to fluorine contents and distributions in these polyacrylates, and the highest stability arises from CF₃ substitutions in the side-chains of the polymers. © 1994 John Wiley & Sons, Inc.     

The syntheses of fluorinated alkanesulfonamides and poly-(fluorinated alkanesulfonamides)

In order to synthesize poly-(fluorinated alkanesulfonamides) a series of model experiments were carried out: (1) reactions of fluorinated alkanesulfonyl fluorides with amines, (2) reactions of fluorinated alkanesulfonyl chloride with amines and (3) reactions of sodium salts of fluorinated alkanesulfonamides with alkyl iodides of fluorinated alkanesulfonic acid esters. Seventeen new fluorinated alkanesulfonamides were prepared in good yields, namely: R_FO(CF₂)₂SO₂NR¹R² (1a-h), R¹R²NSO₂R_FSO₂NR¹R² (2a-h) and [Cl (CF₂)₄O(CF₂)₂SO₂NH(CH₂)₃]₂ (3). Reaction of R_FSO₂NH₂ with equivalent amount of NaOCH₃ and methyl iodide was shown to give both the N-mono- and N,N-di-substituted amides. Consequently the N-monosubstituted alkanesulfonamides were chosen as monomers for syntheses of the poly-(fluorinated alkanesulfonamides) and two new polymers were synthesized. The effect of the condition of the polycondensation on M?_n of the polymers were discussed and elemental composition, ¹⁹F NMR, IR, M?_n, Tg, tensile strength, thermal and chemical stabilities of the polymers were measured. Several new perfluoroalkanesulfonyl chlorides CISO₂R_FSO₂Cl (4a-c) and fluorinated alkanesulfonic acid esters (6a-d) were synthesized. However, reaction of CFCl₂CF₂O(CF₂)₂SO₂F with AlCl₃ was found to give Cl₃CCF₂O(CF₂)₂SO₂F (5) instead of the expected sulfonyl chloride.     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

Über Sn[OCH(CF3)2]2 und Sn (OCH2CF3)2 (n = 1, 2)

On S_n[OCH(CF₃)₂]₂ and S_n(OCH₂CF₃)₂ (n = 1, 2) The sulfoxylates S[OCH(R)CF₃]₂, 1 and 2 and the disulfides S₂[OCH(R)CF₃]₂, 5 and 6 (R = CF₃, H) are obtained by reacting SCl₂ or S₂Cl₂, respectively, and the lithium alcoxides LiOCH(R)CF₃. Chlorine and compound 2 give ClS(O)OCH₂F₃ and CF₃CH₂Cl, whereas the sulfur-sulfur bound is cleaved in 5 and 6 furnishing SCI₂, 1 and 2 , respectively. The ¹⁹F n.m.r. spectrum of 5 and the ¹H n.m.r. spectrum of 6 are interpreted in terms of hindered rotation about the sulfur-sulfur axis.     

Synthesen und Eigenschaften von Tetrakis(perfluoralkyl)tellur Te(Rf)4 (Rf = CF3, C2F5, C2F5, C3F7, C4F9)

Synthesis and Properties of Tetrakis(Perfluoroalkyl)Tellurium Te(R_f)₄ (R_f = CF₃, C₂F₅, C₃F₇, C₄F₉) Te(CF₃)₄ is obtained from the reaction of Te(CF₃)Cl₂ with Cd(CF₃)₂ complexes as a complex with e. g. CH₃CN, DMF. It is a light and temperature sensitive hydrolysable liquid. The reaction with fluorides yields the complex anion [Te(CF₃)₄F]⁻, with fluoride ion acceptors the complex cation [Te(CF₃)₃]⁺. With traces of water an acidic solution is formed. Te(CF₃)₄ acts as a trifluoromethylation reagent. The reaction with XeF₂ gives hints for the formation of Ye(CF₃)₄F₂. Properties and NMR spectra are discussed. The much more stable complexes of Te(R_f)₄ (R_f = C₂F₅, C₃F₇, C₄F₉) are formed from the reaction of TeCl₄ with the corresponding Cd(R_f)₂ complexes.     

Zur Chemie des Xenons, 2. Mitt.: Xenon(II)-fluorid-pentafluoro-orthotellurat,FXeOTeF5 und das System XeF2−CF3COOH

Zusammenfassung Xenon(II)-fluorid-pentafluoro-orthotellurat (Sdp._0,00135°C) entsteht in quantit. Ausb. bei der Reaktion von XeF₂ mit Xe(OTeF₅)₂ im stöchiometrischen Verhältnis 11 und mit geringerer Ausbeute in der Reaktion von XeF₂ mit HOTeF₅ im Verhältnis 11. FXeOTeF₅ ist bis etwa 130°C thermisch stabil. Oberhalb dieser Temp. entsteht unter Xenonentwicklung ein Gemisch von Tellur—Sauerstoff—Fluor-Verbindungen, das noch nicht aufgetrennt werden konnte. Das Infrarot-, Laser-Raman-und¹⁹F-KMR-Spektrum von FXeOTeF₅ wurde untersucht.Im System XeF₂–CF₃COOH [mit HF, CH₃CN und (CF₃CO)₂O als Lösungsmittel] konnten Xenon(II)-fluorid-trifluoroacetat und Xenon(II)-bis(trifluoroacetat) als schwach gelblich gefärbte Festsubstanzen isoliert werden. Beide Verbindungen können ab –20°C bei thermischem oder mechanischem Schock explodieren und zerfallen bei Raumtemp. innerhalb einiger Stdn.; Xe(OOCCF₃)₂ quantitativ zu Xenon, CO₂ und Hexafluoroäthan.

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Xenon Chemistry, II: Xenon(II)-fluoride-pentafluoro-orthotellurate,FXeOTeF ₅, and the SystemXeF ₂–CF₃COOH

Xenon(II)-fluoride-pentafluoro-orthotellurate, FXeOTeF₅ (Bp.53°C; 0,001 Torr), is formed in quantitative yield in the reaction of XeF₂ with Xe(OTeF₅)₂ (molar ratio 11) and with lower yield in the reaction of XeF₂ with HOTeF₅ (molar ratio 11). FXeOTeF₅ is thermally stable up to 130°C. Above this temperature a complex mixture of tellurium—oxygen—fluorine compounds is formed, which has not yet been separated. Infrared-, laser-Raman- and¹⁹F-NMR-spectra are given.Xenon(II)-fluoride-trifluoroacetate and Xenon(II)-bis-(trifluoroacetate) are formed in the system XeF₂–CF₃COOH [with HF, CH₃CN and (CF₃CO)₂O as solvents]. Both compounds are pale yellow solids which can explode above –20°C if thermally or mechanically shocked. They decompose at room temperature within a few hours; Xe(OOCCF₃)₂ giving Xe, CO₂ and Hexafluoroethane quantitatively.

     

Syntheses of novel delocalized cations and fluorinated anions,new fluorinated solvents and additives for lithium ion batteries

To improve the properties of rechargeable lithium ion batteries, like conductivity, SEI-formation, thermal and electrochemical stability, low and high temperature performance and safety new electrolyte salts, novel solvents (co-solvents) and additives have been synthesized. All new anions, solvents and additives contain fluorine proving the importance of this element for the electrolyte system. Tetrafluoroborates having bulky delocalized nitrogen-, phosphorus and sulfur-centered counter-cations containing tetramethylguanidyl substituents, like [(Me₂N)₂CNC(NMe₂)₂]⁺, have been prepared to improve the conductivity in polymer electrolytes. The hitherto unknown lithium sulfonate, MeOCF₂CF₂SO₃Li, has been successfully synthesized along with further analogs, and also MeOCF₂CF(CF₃)SO₃Li was obtained, both from precursors, FO₂SCF₂C(O)F or FO₂SCF(CF₃)C(O)F accessible by ring opening reactions from the respective sultones. For the lithium salt CF₃OCF(CF₃)SO₃Li, a new simple synthetic pathway was found where CF₃OCFCF₂ and SO₂F₂ were used as precursors. Novel possible redox shuttles, namely (CF₃)₅C₆OLi and fluorinated pyridine-N-oxides have been prepared. A neutral cyclic carben-PF₅ adduct turned out to be a very effective overcharge protection additive. The family of cyclic and acyclic carbonates playing a key-role as electrolyte solvents in lithium ion batteries could be extended by derivatives of 1,1,1,4,4,4-hexafluorobutandiol. Reaction products from perfluoropropene oxide and alcohols, ROC(F)CF₃C(O)OR (R = CH₂CF₃, CH₂CH₂, CH(CF₃)₂) were obtained according to new optimized methods. New cyclic sulfonamides synthesized from FO₂SCF₂C(O)F and FO₂SCF(CF₃)C(O)F could be successfully identified as versatile electrolyte additives.     

Syntheses and Structures of F6XeNCCH3 and F6Xe(NCCH3)2

Acetonitrile and the potent oxidative fluorinating agent XeF₆ react at ?40 °C in Freon‐114 to form the highly energetic, shock‐sensitive compounds F₆XeNCCH₃ ( 1 ) and F₆Xe(NCCH₃)₂?CH₃CN ( 2 ?CH₃CN). Their low‐temperature single‐crystal X‐ray structures show that the adducted XeF₆ molecules of these compounds are the most isolated XeF₆ moieties thus far encountered in the solid state and also provide the first examples of Xe^VI? N bonds. The geometry of the XeF₆ moiety in 1 is nearly identical to the calculated distorted octahedral (C_3v) geometry of gas‐phase XeF₆. The C_2v geometry of the XeF₆ moiety in 2 resembles the transition state proposed to account for the fluxionality of gas‐phase XeF₆. The energy‐minimized gas‐phase geometries and vibrational frequencies were calculated for 1 and 2 , and their respective binding energies with CH₃CN were determined. The Raman spectra of 1 and 2 ?CH₃CN were assigned by comparison with their calculated vibrational frequencies and intensities.     

C6F5XeF, a versatile starting material in xenon-carbon chemistry

The molecules Ar_FXeF (Ar_F=C₆F₅, 2,4,6-C₆H₂F₃) with a more polar Xe-F bond than XeF₂ are versatile starting materials for substitution reactions. Fluorine-aryl substitutions with Cd(Ar_F)₂, C₆F₅SiMe₃/[F]⁻, and C₆F₅SiF₃ formed symmetric and/or asymmetric diarylxenon compounds. Applying C₆F₅BF₂, with a higher F⁻-affinity than the corresponding aryltrifluorosilane, in contrast gave the salt [RXe] [Ar_FBF₃]. Using the alkenyl and alkyl compounds CF₂=CFSiMe₃/[F]⁻, CF₃SiMe₃/[F]⁻, and Cd(CF₃)₂ in reactions with C₆F₅XeF, the perfluoroalkenyl or -alkyl transfer reagents were consumed without observing C₆F₅XeCF=CF₂ or C₆F₅XeCF₃ but the formation of Xe(C₆F₅)₂ (dismutation product) and in the latter case C₆F₅CF₃ (coupling product), gave hints of the desired intermediates.