C(CF3)2OH → OCH(CF3)2 Isomerism in some sulfur and phosphorus compounds

The insertion of (CF₃)₂CO into the PH bond of Me_nH_3?nP yields Me_nH_2?nPC(CF₃)₂OH and Me_nH_1?nP[C(CF₃)₂OH]₂ (n=O, 1), respectively [1]. MeP[C(CF₃)₂OH]₂ rearranges giving the diphosphine [MePOCH(CF₃)₂]₂ and the phosphorane MeP[OCH(CF₃)₂]₄. Me₂PH reacts with (CF₃)₂CO forming several products, e.g. MePF[OCH(CF₃)₂]₂ and Me₂PPMe₂ [1]. The phosphines tBu(R)PH(R=Me, tBu), however, add (CF₃)₂CO giving rise to the phosphinites tBu(R)POCH(CF₃)₂, which furnish stable phosphonium salts upon treating with MeI. (CF₃)₂CO inserts into the SH bond of RSH to yield RSC(CF₃)₂OH (R=H,Me,Ph), which were reacted with MeI, too. Reacting SCl₂ with LiOCH(CF₃)₂ gives S[OCH(CF₃)₂]₂ which is oxidised by chlorine to the sulfurane ClS[OCH(CF₃)₂]₃ [2]. The sulfurane is able to transfer (CF₃)₂CHO groups to phosphorus (III) compounds, e.g. P[OCH(CF₃)₂]₃ and Me₃P yielding P[OCH(CF₃)₂]₅ and [Me₃POCH(CF₃)₂]⁺Cl^?. ClS[OCH(CF₃)₂]₃ gives a stable salt upon reaction with SbCl₅, like ClP[OCH(CF₃)₂]₄. The mechanisms for these reactions are discussed.     

Reactions of Trifluoronitrosomethane with bistrifluoromethylphosphorus compounds, (CF3)2PX (where x = H,Cl, CF3)

Trifluoronitrosomethane reacts with bis(trifluoromethyl)phosphine to give (CF₃)₂P(O)N(OH)CF₃ and a small amount of (CF₃)₂NOH. On the other hand, the reactions with tris(trifluoromethyl)phosphine and bis(trifluoromethyl)chlorophosphine afford (CF₃)₂NOP(O)CF₃N(CF₃)₂ and (CF₃)₂NP(O)(CF₃)Cl respectively. Isomerisation of

may be involved as found for the isomerisation of the phosphine, (CF₃)₂NOP(CF₃)₂, to the phosphoryl compound, (CF₃)₂NP(O)(CF₃)₂. Mechanisms for the above reactions are discussed.     

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.     

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.     

Pentafluoro-λ-sulfanyl (SF5) perfluoroalkyl iodides-synthesis and reaction with ethylene and tetrafluoroethylene : Crystal structure of SF5(CF2)4CH2CH2I

A series of reactions between SF₅CF₂CF₂I and SF₅(CF₂)₄I with F₂CCF₂ was carried out in an effort to find the most effective methods for chain-extension. Also, for the first time, SF₅(CF₂)₈I and SF₅(CF₂)₁₀I have been prepared and isolated. The reaction conditions for the addition of H₂CCH₂ were also investigated. A determination of the crystal structure of the SF₅(CF₂)₄CH₂CH₂I has been carried out: the crystal system is monoclinic, with space group P2(1)/n and a=23.465(5) Å; b=6.0971(12) Å; c=44.892(9) Å; α=90°; β=99.38(3)°; γ=90°; Z=20.     

Derivatives of trifluorovinylsulfur pentafluoride (SF5CFCF2) II

Trifluorovinylsulfur pentafluoride (SF₅CFCF₂) and carbonyl fluoride will add, in the presence of cesium fluoride and acetonitrile, to form SF₅CF(CF₃)C(O)F. This new acid fluoride serves as a source for preparing derivatives containing the SF₅CF(CF₃) - grouping. The following new compounds have been prepared and characterized: SF₅CF(CF₃)X where X = C(O)F, C(O)CH₃, C(O)OH, C(O)NH₂, CN. The dimer, (SF₅CFCF₂)₂, has also been prepared. Infrared, mass, and nmr spectra are presented in order to support their proposed structure.     

A new catalytic system for the copolymerization of dicyclopentadiene with CO: PdCl2/phen/M(CF3SO3)n

A new three-component catalytic system, PdCl₂/phen/M(CF₃SO₃)_n, was studied in the copolymerization of dicyclopentadiene (DCPD) with CO. It was found that the PdCl₂/phen/CF₃SO₃H catalytic system gave a very low catalytic activity, and the PdCl₂/phen/M(CF₃SO₃)_n catalytic system exhibited high activity when M(CF₃SO₃)_n was introduced instead of CF₃SO₃H. The resultant cooligomer was analyzed using various techniques such as FT-IR, ¹H NMR, ¹³C NMR, DSC and TGA. The results indicated that the copolymer was a polyspiroketal (PS) of CO and DCPD. Due to the tension of the ring of DCPD, the degree of copolymerization is low and the degree of crystallinity is also not high. The effects of ligands, M(CF₃SO₃)_n, solvents, 1,4-benzoquinone/PdCl₂ molar ratio, and temperatures on the copolymerization have been discussed in detail. The results showed that this novel catalytic system exhibited highly efficient activity, especially when 1,10-phenanthroline (phen) was used as ligand and Cu(CF₃SO₃)₂ was used as cocatalyst. The corresponding reaction rate was 49 000 g PS/molPd h when the reaction was carried out at 60 °C and 3.0 MPa of CO. The weight average molecular weight (M_w) and the number average molecular weight (M_n) of the resultant cooligomer were 1180 g/mol and 564 g/mol, respectively.     

Reactivite d'alcynes fluores vis-a-vis de methylthiolates [(η5-C5H5)M(SMe)(CO)3] et d'hydrures [(η5-C5H5)MH(CO)3] de molybdene et de tungstene

The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- $\text{MoC(O)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [Cp(OC)₂$\text{MC(CF}{}_3\text{)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [CpW(CO)₃C(CF₃C(CF₃)SMe], [CpW{η³-$\text{C(CF}{}_3\text{)C(CF}{}_3\text{)C(SMe)OC}$(O)}-(CO)₂]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF₃CCCF₃ [CpMH(CO)₃] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)₃C(CF₃)C(CF₃)H]and an isomer of undetermined structure.     

gem-Difluoroallyllithium: Preparation by the transmetalation procedure and some reactions

3,3-Difluoroallyltrimethyltin has been prepared by the reaction of β-trimethylstannylethylidenetriphenylphosphorane with chlorodifluoromethane. This tin compound reacts with n-butyllithium in tetrahydrofuran at -95°C to generate gem-difluoroallyllithium. The latter, however, is not stable in solution at that temperature. If generated in situ in the presence of a triorganochlorosilane, products of the type R₃SiCF₂CHCH₂ are obtained in good yield. Addition to the CO bond of 3-pentanone to give (C₂H₅)₂C(OH)CF₂CHCH₂ was achieved by the method of alternate, incremental additions.     

Stereodivergent synthesis of novel chiral C2-symmetric bis-trifluoromethyl-2-oxazolidinones

A simplified effective synthetic process is described for the diastereoselective synthesis of the chiral C₂-symmetric CF₃-ureas (R,R)-15 and (S,S)-15 from (S)-α-phenylethylamine, glyoxal and CF₃I.     

Stereoselective generation of cis-2-lithio-3-CF3-oxirane via CF3-substituted β-oxido carbenoids. Highly stereoselective synthesis of CF3-substituted tri- and tetrasubstituted oxiranes and tetrasubstituted alkenes

Treatment of 2-substituted 3,3-dichloro-1,1,1-trifluoropropan-2-ols with organolithium reagents R²Li in THF at −98°C stereoselectively produces 2,3-disubstituted 2-lithio-3-trifluoromethyloxiranes with Li and CF₃cis. The reagents react with electrophiles El-X or organoboranes R³BR₂ to give CF₃-containing tri- and tetrasubstituted oxiranes or tetrasubstituted alkenes, respectively, with high diastereoselectivities.     

Nitroxide chemistry. Part XIX. Reaction of bistrifluoromethyl nitroxide with diphenylketene and related compounds (Ph2CHCOX,X  OH,Cl, NH2)

The following reactions have been accomplished: 2(CF₃)₂NO· + Ph₂CCO → Ph₂C[ON(CF₃)₂]CO₂N(CF₃)₂ → (on hydrolysis) Ph₂C[ON(CF₃)₂]CO₂H; 2 (CF₃)₂NO· + Ph₂CHCOX → (CF₃)₂NOH + Ph₂C[ON(CF₃)₂]COX (X  OH, Cl,NH₂).     

[Co(en)3][In3(H2PO4)6(HPO4)3]·H2O: A new layered indium phosphate templated by cobalt complex

A new layered indium phosphate [Co(en)₃][In₃(H₂PO₄)₆(HPO₄)₃]·H₂O (1) has been synthesized solvothermally by using a racemic mix of chiral metal complex Co(en)₃Cl₃ as a template. Its structure is determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, NMR and TG analyses. The inorganic layer is built up by alternation of In-centred octahedra (InO₆) and P-centered tetrahedra (PO₃(OH), PO₂(OH)₂, PO₂(=O)(OH) and PO(=O)(OH)₂) forming a 4.12-net. The metal complex cations locate in the interlayer region and interact with the host network through H-bonds. It is the first indium phosphate compound templated by a transition-metal complex and is isostructural with GaPO-CJ14. Crystal data: 1, monoclinic, space group P2₁/m (No. 11), a=9.1700(18) Å, b=22.6923(5) Å, c=9.9116(2) Å, β=107.87(3)°, Z=4, R_1[I>2σ(I)]=0.0287 and wR_{2(all data)}=0.0939.     

A simple and highly efficient synthesis of N-phenyl-2-polyfluoroalkyl-4-quinolones from 2-anilinoacetophenone and RFCO2Et

The condensation of 2-anilinoacetophenone with R_FCO₂Et (R_F = CF₂H, CF₃, C₂F₅) in the presence of LiH in THF affords the corresponding N-phenyl-2-polyfluoroalkyl-4-quinolones in excellent yields.     

Syntheses and crystal structures of two new hydrated borates, Zn8[(BO3)3O2(OH)3] and Pb[B5O8(OH)]·1.5H2O

Two new hydrated borates, Zn₈[(BO₃)₃O₂(OH)₃] and Pb[B₅O₈(OH)]·1.5H₂O, have been prepared by hydrothermal reactions at 170 °C. Single-crystal X-ray structural analyses showed that Zn₈[(BO₃)₃O₂(OH)₃] crystallizes in a non-centrosymmetric space group R32 with a=8.006(2) Å, c=17.751(2) Å, Z=3 and Pb[B₅O₈(OH)]·1.5H₂O in a triclinic space group P1¯ with a=6.656(2) Å, b=6.714(2) Å, c=10.701(2) Å, α=99.07(2)°, β=93.67(2)°, γ=118.87(1)°, Z=2. Zn₈[(BO₃)₃O₂(OH)₃] represents a new structure type in which Zn-centered tetrahedra are connected via common vertices leading to helical ribbons _∞¹[Zn₈O₁₅(OH)₃]¹⁷⁻ that pack side by side and are further condensed through sharing oxygen atoms to form a three-dimensional _∞³[Zn₈O₁₁(OH)₃]⁹⁻ framework. The boron atoms are incorporated into the channels in the framework to complete the final structure. Pb[B₅O₈(OH)]·1.5H₂O is a layered compound containing double ring [B₅O₈(OH)]²⁻ building units that share exocyclic oxygen atoms to form a two-dimensional layer. Symmetry-center-related layers are stacked along the c-axis and held together by interlayer Pb²⁺ ions and water molecules via electrostatic and hydrogen bonding interactions. The IR spectra further confirmed the existence of both triangular BO₃ and OH groups in Zn₈[(BO₃)₃O₂(OH)₃], and BO₃, BO₄, OH groups as well as guest water molecules in Pb[B₅O₈(OH)]·1.5H₂O.     

[Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3], crystal structure and comparison with uranium minerals with U3O8-type sheets

The new U(VI) compound, [Ni(H₂O)₄]₃[U(OH,H₂O)(UO₂)₈O₁₂(OH)₃], was synthesized by mild hydrothermal reaction of uranyl and nickel nitrates. The crystal-structure was solved in the P-1 space group, a=8.627(2), b=10.566(2), c=12.091(4) Å and α=110.59(1), β=102.96(2), γ=105.50(1)°, R=0.0539 and wR=0.0464 from 3441 unique observed reflections and 151 parameters. The structure of the title compound is built from sheets of uranium polyhedra closely related to that in β-U₃O₈. Within the sheets [(UO₂)(OH)O₄] pentagonal bipyramids share equatorial edges to form chains, which are cross-linked by [(UO₂)O₄] and [UO₄(H₂O)(OH)] square bipyramids and through hydroxyl groups shared between [(UO₂)(OH)O₄] pentagonal bipyramids. The sheets are pillared by sharing the apical oxygen atoms of the [(UO₂)(OH)O₄] pentagonal bipyramids with the oxygen atoms of [NiO₂(H₂O)₄] octahedral units. That builds a three-dimensional framework with water molecules pointing towards the channels. On heating [Ni(H₂O)₄]₃[U(OH,H₂O)(UO₂)₈O₁₂(OH)₃] decomposes into NiU₃O₁₀.     

(CF3)2Cd·D und (CF3)2Zn·D: neue reagenzien für difluorcarben-reaktionen [1]

During the thermal decomposition of (CF₃)₂Cd and (CF₃)₂Zn complexes primarily difluorocarbene is eliminated. The formation of CF₂ is unambiguously proved by matrix i.r. spectroscopy. Both (CF₃)₂Cd·D and (CF₃)₂Zn·D are excellent CF₂ sources, which can easily be prepared and handled, and which undergo CF₂ reactions even at low temperature. CF₂ insertion was found during the reaction of (CF₃)₂Te with (CH₃)₂Cd via the intermediate formation of a CF₃Cd compound to form CH₃TeCF₂CH₃. (CF₃)₂Cd·glyme reacts with (CH₃)₃Si(OCOCF₃) to CF₃Cd(OCOCF₃)·glyme; during this reaction CF₂ is also eliminated.     

Synthesis and characterization of a new layered gallium phosphate [Co(en)3][Ga3(H2PO4)6(HPO4)3] templated by cobalt complex

A new layered gallium phosphate [Co(en)₃][Ga₃(H₂PO₄)₆(HPO₄)₃], denoted as GaPO-CJ14, has been synthesized solvothermally by using a racemic mix of chiral metal complex Co(en)₃Cl₃ as a template. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The compound crystallizes in the monoclinic space group P2₁/m (No. 11) with a=9.2103(3), b=22.0936(8), c=9.5458(4) Å, β=108.278(2)°, Z=2, R₁=0.0497 and wR₂=0.1122 for all data. The inorganic layer is built up by alternation of Ga-centered octahedra (GaO₆) and P-centered tetrahedra (PO₃(OH), PO₂(OH)₂ , PO₂(O)(OH) and PO(O)(OH)₂) forming a 4.12-net. The sheet structure is featured by a series of structural units composed of two centrosymmetrically related [3.3.3] propellane-like chiral motifs. The metal complex cations locate in the interlayer region and interact with the host network through H-bonds.     

Absolute rate constants for the reactions ofOHradicals withCH3CH2OH, CF2HCH2OHandCF3CH2OH

Summary Pulsed laser photolysis with resonance fluorescence monitoring of OH radicals was applied at T = 300±2 K to obtain the rate constants of k₁= (3.38±0.60)x10^-12, k₂= (2.52±0.44)x10^-13and k₃ = (1.06±0.30)x10^-13cm³molecule^-1s^-1with 2σprecision given for the overall reactions OH + CH₃CH₂OH (1), OH + CF₂HCH₂OH (2) and OH + CF₃CH₂OH (3), respectively. k₂is the first direct kinetic data for the reaction of OH radicals with CF₂HCH₂OH reported in the literature.</o:p>     

Cyclometalated N,N-dimethylbenzylamine ruthenium(II) complexes [Ru(C6HRRR-o-CH2NMe2)(bpy)(RCN)2]PF6 for bioapplications: synthesis, characterization, crystal structures, redox properties, and reactivity toward PQQ-dependent glucose dehydrogenase

Cyclometalated derivatives of ring-substituted N,N-dimethylbenzylamines with controlled redox potentials as potent mediators of bioelectrochemical electron transport are reported. The cycloruthenation of R¹R²R³C₆H₂CH₂NMe₂ (R¹, R², R³ = H, Me, ^tBuO, MeO, NMe₂, F, CF₃, CN, NO₂) by [(η⁶-C₆H₆)RuCl(μ-Cl)]₂ in the presence of NaOH/KPF₆ in acetonitrile or pivalonitrile affords cyclometalated complexes [(η⁶-C₆H₆)Ru(C₆HR¹R²R³-o-CH₂NMe₂)(RCN)]PF₆ [R = Me (1) and R = CMe₃ (2)] in good yields. Reactions of complexes 1 and 2 with 2,2′-bipyridine (bpy) in acetonitrile or pivalonitrile result in dissociation of η⁶-bound benzene and the formation of [Ru(C₆HR¹R²R³-o-CH₂NMe₂)(bpy)(RCN)₂]PF₆ [R = Me (3) and R = CMe₃ (4)]. All new compounds have been fully characterized by mass spectrometry, ¹H/¹³C NMR, and IR spectroscopy. An X-ray crystal structural investigation of complex 1 (R¹/R²/R³ = H/H/H) and two complexes of type 3 (R¹/R²/R³ = MeO/H/H, MeO/MeO/H) has been performed. Acetonitrile ligands of 3 are mutually cis and the σ-bound carbon is trans to one of the bpy nitrogens. Measured by the cyclic voltammetry in MeOH as solvent, the redox potentials of complexes 3 for the Ru^II/III feature cover the range 320-720 mV (versus Ag/AgCl) and correlate linearly with the Hammett constants. Complexes 3 mediate efficiently the electron transport between the active site of PQQ-dependent glucose dehydrogenase (PQQ = pyrroloquinoline quinone) and a glassy carbon electrode. Determined by cyclic voltammetry the second order rate constant for the oxidation of the reduced (by d-glucose) enzyme active site by Ru^III derivative of 3 (R¹/R²/R³ = H) (generated electrochemically) is as high as 4.8 × 10⁷ M⁻¹ s⁻¹ at 25 °C and pH 7.