Anionic derivatives of pentafluoro-λ-sulfanyl (fluorosulfonyl) acetic acid esters

New ester salts [R₃NH]⁺[F₅SC(SO₂F)C(O)OR′]⁻ where RH, CH₃CH₂ and R′CH₃,(CH₃)₂CH have been prepared from corresponding esters and amines. The sodiumsalt Na[F₅SC(SO₂F)C(O)OCH(CH₃)₂] was used to prepare the following -substitutedderivatives: SF₅CX(SO₂F)C(O)OCH(CH₃)₂, XBr, Cl. The crystal structure of[(C₂H₅)₃NH]⁺[F₅SC(SO₂F)C(O)OCH₃]⁻ was determined and is monoclinic: P2₁/n;a=8.758(2) Å, b=9.645(2) Å and c=19.167(4) Å; β=97.92(3)°; V=1603.6 ų; Z=4.     

Structures and conformations of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2

The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF₃SO₂)₂O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF₃SO₂)₂CF₂ have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C₂ symmetry and one with C₁ symmetry. In both compounds structures with C₂ symmetry and dihedral angles SOSC ≈ 100° ((CF₃SO₂)₂O) and SCSC ≈ 150° ((CF₃SO₂)₂CF₂) are lowest in energy. According to the GED analyses the dominant conformer of (CF₃SO₂)₂O possesses C₂ symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF₃SO₂)₂CF₂ only one conformer with C₂ symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.     

Reactions of fluorinated acid anhydrides, (CF3CO)2O, (CF3SO2)2O and (FSO2)2O, with organometallic substrates of group 15 (As, Sb and Bi)

(C₆H₅)₃MX₂ (M = As, Sb; X = OCOCF₃ and M = Sb, Bi; X = SO₃F, SO₃CF₃) compounds prepared by the interaction of triphenylmetal(V) substrates with (CF₃CO)₂O, (CF₃SO₂)₂O and (FSO₂)₂O have been characterized by molecular weight determination, elemental and spectroscopic (IR, ¹H and ¹⁹F NMR, mass) analyses.     

Polymer chemistry. Part 1. Model compounds related to hexafluoropropenevinylidene fluoride elastomer

Model compounds related to the important elastomer derived from CH₂2=CF₂/CFCF₃ are synthesised from telomers (CF₃)₂CF(CH₂CF_2nI, by coupling and by fluorodeiodination reactions. These models, in reactions with bases, give information relating to mechanism of cross-linking of the polymer and indications of factors that limit its working life. Novel use of SbF₅ for dehydrofluorination in synthesis of fluorinated mono-enes and di-enes is described.     

CH3CF2O2与HO2自由基反应机理的理论研究

用密度泛函理论(DFT)的B3LYP方法，在6-311G、6-311+G(d)、6-311++G(d, p) 基组水平上研究了CH₃CF₂O₂与HO₂自由基反应机理. 结果表明, CH3CF₂O₂与HO₂自由基反应存在两条可行的通道. 通道CH3CF₂O₂＋HO₂→IM1→TS1→CH₃CF₂OOH＋O₂的活化能为77.21 kJ•mol^－1，活化能较低，为主要反应通道，其产物是O₂和CH₃CF₂OOH. 这与实验结果是一致的；而通道CH₃CF₂O₂＋HO₂→IM2→TS2→IM3→TS3→IM4＋IM5→IM4＋TS4→IM4＋OH＋O₂→TS5＋OH＋O₂→CH₃＋CF₂O＋OH＋O₂→CH₃OH＋CF₂O＋O₂的控制步骤活化能为93.42 kJ•mol^－1，其产物是CH₃OH、CF₂O和O₂. 结果表明这条通道也能发生，这与前人的实验结果一致.     

Structures and conformations of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2

The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF₃SO₂)₂O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF₃SO₂)₂CF₂ have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C₂ symmetry and one with C₁ symmetry. In both compounds structures with C₂ symmetry and dihedral angles SOSC ≈ 100° ((CF₃SO₂)₂O) and SCSC≈ 150° ((CF₃SO₂)₂CF₂ are lowest in energy. According to the GED analyses the dominant conformer of (CF₃SO₂)₂O₂ possesses C₂ symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF₃SO₂)₂CF₂ only one conformer with C₂ symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.     

The excess molar volumes of (an alkanol + a branched chain ether) at the temperature 298.15 K and the application of the ERAS model

The excess molar volumes V_m^E {x(CH₃OH or CH₃CH₂OH or CH₃(CH₂)₂OH or CH₃CH(OH)CH₃ + (1 - x){CH₃(CH₂)₂}₂O or CH₃C(CH₃)₂OCH₃ or CH₃CH₂C(CH₃)₂OCH₃} have been calculated from measured values of density over the whole composition range at the temperature 298.15 K in order to investigate OH … O specific interactions. The results are explained in terms of the strong self-association of the alkanols, the specific interaction between the alkanol, and the ether molecules and packing effects upon mixing. The experimental V_m^h results presented here, together with the previously reported data for the molar excess enthalpy H_m^E, has been used to test the Extended Real Associated Solution (ERAS) model.     

Synthetic utility of 3-(perfluoro-1,1-dimethylbutyl)-1-propene. Part IV. Synthesis and properties of 1,1,1,2,2,3,3,8,9,9,9-undecafluoro-4,4,8-tris(trifluoromethyl)nonane - a new potential oxygen carrier for biomedical use

The title compound, CF₃CF₂CF₂(CF₃)₂CCH₂CH₂CH₂CF(CF₃)₂, was synthesised in high yield by a free radical addition of heptafluoroisopropyl iodide to 3-(perfluoro-1, 1-dimethylbutyl)-1- propene followed by reduction of the adduct. Physical properties and solubilities for oxygen, nitrogen, carbon dioxide and air of the new fluorohydrocarbon have been determined.     

Allylstannation V. cis-stereoconvergent sysnthesis of homoallylic alcohols and 4-chloro-2,6-dialkyl-3-methyltetrahydro-pyrans by the addition reaction of 1-buten-3-yldichloro-n-butyltin and aldehydes

1-Buten-3-yl-n-butyldichlorotin, generated in situ by redistribution of (E/Z)-2-butenyltri-n-butyltin and BuSnCl₃, reacts readily with neat RCHO (R = CH₃, C₂H₅, (CH₃)₂CH) at 25°C to give linear alcohols RCH(OH)CH₂CH---CHCH₃ and/or 2,3,4,6-tetrasubstituted tetrahydropyrans, CH₂CH(R)OCH(R)CH(CH₃)CH-(Cl), which are mainly in the cis-configuration with respect to the CH(CH₃)-CH(Cl) bond. When R = (CH₃)₃C and C₆H₅, only the homoallylic alcohols are obtained. These cis-stereoconvergent syntheses are explained in terms of kinetic control of the formation of adducts obtained by insertion of one or two aldehyde molecules into the organotin substrate.     

Synthesis and characterization of Na5[Co(CO)3(P{(CH2)nC6H4-P-SO3}3)2], n = 1, 2, 3, and 6. Novel zwitterion

The electron donating water soluble phosphines, P{(CH₂)nC₆H₄-p-SO₃Na}₃,n = 1, 2, 3 and 6, react rapidly with Co₂(CO)₈ under two phase reaction conditions to yield the disproportionation products, [Co(CO)₃(P{(CH₂)nC₆H₄-p-SO₃Na₃}₂] [Co(CO)₄]. Selective precipitation yields the formally zwitterionic complex anions as the sodium salt, [Co(CO)₃(P{(CH₂)nC₆H₄-p-SO₃} ₃)₂]⁵⁻. The anions can be used as precursors to water soluble cobalt hydroformylation catalysts under two phase and supported aqueous phase conditions. The tendency to form alcohol products is low with these complexes. The behavior of the catalysts is consistent with an active species that remains water soluble during the reaction and is not leached into the nonaqueous phase.     

The Reaction of Sodium Perfluoroalkanesulfinate with PCl3

The reaction between sodium perfluoroalkanesulfinate(1)(Rf=a, Cl(CF₂)₄;b, Cl(CF₂)6;c, Cl(CF₂)₈;d, n-C₆F₁₃;e, n-C₈F₁₇;f, H(CF₂)₄OCF₂CF₂)andphosphorus trichloride in acetonitrile at 0℃ resulted in the formation of anunstable intermediate, which was hydrolysed directly with aqueous sodium hydro-xide solution to give the corresponding perfluorocarboxylic acid in good yield.     

Imido complexes of molybdenum and tungsten(VI); X-ray crystal structure of cis-(η-CF3SO3)2 W(NBu)2(NH2Bu)2

The synthesis of the homoleptic molybdenum imido compound Li₂Mo(NBu^t)₄ is reported. The complexes M (NBu^t)₂(NHBu^t)₂ (M = Mo, W) can be protonated with various strong acids giving neutral species. The X-ray crystal structure of the tungsten complex W (NBu^t)₂(NH₂Bu^t)₂ (SO₃CF₃)₂ confirms the presence of O-coordinated cis- CF₃SO₃ groups.     

New dense fluoroalkyl-substituted imidazolium ionic liquids

New mono and polyfluoroalkyl-substituted ionic liquids have been synthesized and characterized. The neat reaction of 1-methylimidazole (1a) with 1,1,1-trifluoro-3-iodopropane (2a) at 80°C formed the quaternary salt, 1-methyl-3-trifluoropropylimidazolium iodide (3), in 90% yield. Similarly, sodium imidazole (1b) gave good yields of the quaternary salts, 1,3-bis(trifluoropropyl)imidazolium iodide (3b) with an excess of 2a, and 1,3-bis(monofluoropropyl)imidazolium bromide (3c) with an excess of 1-fluoro-3-bromopropane (2b). In water as solvent, metathesis reactions of 3 with KPF₆, LiN(SO₂CF₃)₂ and KSO₃CF_3, and of 3b and 3c with KPF₆ and LiN(SO₂CF₃)₂ led to 4a–c, 4d,e, and 4f,g, respectively, in good isolated yields. Some of the di(polyfluoroalkyl)imidazolium salts are liquids with densities in excess of 1.8 g/cm³.     

Kinetische und mechanistische untersuchungen von Übergangsmetall-komplex-reaktionen : III. Abhängigkeit des gleichgewichts der addition von tributylphosphan an pentacarbonyl(arylmethoxycarben)wolfram vom substituenten am ring

The reaction of pentacarbonyl(arylmethoxycarbene)tungsten, (CO)₅W[C(OCH₃(p-C₆H₄R)] [R = OCH₃ (a), CH₃ (b), H (c), Br (d), CF₃ (e)], with tributylphosphane at low temperatures results in a reversible addition of the phosphane to the carbene carbon atom. The addition—dissoziation equilibrium is not only dependent on the temperature but also to a strong degree on the nature of the substituent R. ΔG, ΔH and the equilibrium constant K increase in the series from R = OCH₃ to R = CF₃. With the exception of R = OCH₃ the substituents b to e form an isentropic class. For all substituents (a to e) a linear dependency from Jaffés σ-constants was observed for ΔH. Good linear correlation for the substituents b to e was also found for log K and σ as well as for log K and the CO-force constants k_cis and k_trans.     

Organoplatinum(IV) compounds : II. Preparation and characterization of trimethylplatinum(IV) compounds with chelating nitrogen donor ligands. The crystal and molecular structure of iodotrimethyl[bis(3,5-dimethyl-1-pyrazolyl)methane]platinum(IV)

Compounds of the types Me₃PtX(NN) (where X = Cl, I, OAc, NO₃; NN = bis(1-pyrazolyl)methane (pz₂CH₂), bis(3,5-dimethyl-1-pyrazolyl)methane ((Me₂pz)₂CH₂), or bis(2-pyridyl)methane (py₂CH₂)), [Me₃Pt(NNN)][PF₆] (where NNN=tris(1-pyrazolyl)methane (pz₃CH), or tris(2-pyridyl)methane (py₃CH)), and [Me₃Pt((Me₂pz)₂CH₂(py)][PF₆] have been prepared and characterized by elemental analyses and ¹H and ¹³C NMR spectroscopy; the structure of Me₆PtI[(Me₂pz)₂CH₂] (1) has also been determined by X-ray crystallography. Crystals of 1 are orthorhombic, space group Pcmn with four molecules in a unit cell of dimensions a 11.936(5), b 14.462(4), c 10.138(5) Å. The structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations to R = 0.022 for 1719 observed data. The molecule has crystallographic mirror symmetry. The Pt atom has octahedral geometry with one methyl group trans to iodine and two methyl groups trans to the N atoms of the bidentate ligand (Pt---I 2.843(1), Pt---N, 2.236(4), Pt---C 2.077(6) (trans to I) and 2.032(5) Å (trans to N)).     

Synthesis and chemistry of the bis(trimethylsilyl)amido bis-tetrahydrofuranates of the group 2 metals magnesium, calcium, strontium and barium. X-ray crystal structures of Mg[N(SiMe3)2]2·2THF and related Mn[N(SiMe3)2]2·2THF

Transamination reactions utilizing the compound mercuric bis(trimethylsilyl)amide, Hg{N(SiMe₃)₂}₂, in tetrahydrofuran (THF), and the metals Na, Mg, Ca, Sr, Ba and Al have been investigated. Thus the THF solvated compounds Na[N(SiMe₃)₂]·THF and M[N(SiMe₃)₂]₂·2THF, M = Mg, Ca, Sr and Ba (1–4), have been prepared. The X-ray crystal structures of 1 and the related manganese compound Mn[N(SiMe₃)₂]₂·2THF (5) are reported. Interaction of the silylamides, 2–4, with a range of crown ethers apparently proceeded with elimination of silylamine, (Me₃Si)₂NH, and novel ring opening of the crown ethers, generating species containing a donor alkoxide ligand with a vinyl ether function, presumably, ---O(CH₂CH₂O)_nCH=CH₂ (n = 3−5). The silylamides 2–4 were also cleanly converted to the corresponding alkoxides (from ¹H NMR data) in reactions with stoichiometric quantities of 3-ethyl-3-pentanol.     

O- versus F-protonation in (CF3CF2)2O and CF3OCF(CF3)2: a preliminary theoretical study

The relative modifications induced in the structure of perfluorodiethyl ether (CF₃CF₂)₂O and perfluoroisopropyl methyl ether CF₃OCF(CF₃)₂ by oxygen and fluorine protonation are studied at the RHF level with the 3–21G basis and correlated with their proton affinities and dissociation energies.     

Synthesis, characterization and antitumor activity of some arylantimony triphenylgermanylpropionates and crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2]2Sb(4-ClC6H4)3

A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph₃GeCHR¹CHR²CO₂)_nSbAr_(5−n) (R¹=H, Ph; R²=H, CH₃; n=1, 2) were synthesized and characterized by elemental analysis, IR, ¹H-NMR, ¹³C-NMR and mass spectroscopy. The crystal structures of Ph₃GeCH(Ph)CH₂CO₂SbPh₄ and [Ph₃GeCH₂CH(CH₃)CO₂]₂Sb(4-ClC₆H₄)₃ were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported.     

Synthesis, characterization of new Rh---Co mixed-metal clusters and reactions of clusters containing [Rh2Co2C2] core with 1-alkynes and/or carbon monoxide

Six new cluster derivatives [Rh₂Co₂(CO)₆(μ-CO)₄(μ₄,η²-HCCR)] (R=FeCp₂ 1, CH₂OH 2, (CH₃O)C₁₀H₆CH(CH₃)COOCH₂CCH 3) and [RhCo₃(CO)₆(μ-CO)₄(μ₄,η²-HCCR)] (R=FeCp₂ 4, CH₂OH 5, (CH₃O)C₁₀H₆CH(CH₃)COOCH₂CCH 6) were obtained by the reactions of [Rh₂Co₂(CO)₁₂] and [RhCo₃(CO)₁₂] with substituted 1-alkyne ligands HCCR [R=FeCp₂ 7, CH₂OH 8, (CH₃O)C₁₀H₆CH(CH₃) COOCH₂CCH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co---Co bond of the tetranuclear clusters to give butterfly clusters. [Rh₂Co₂(CO)₆(μ-CO)₄(μ₄,η²-HCCFeCp₂)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co₂(CO)₆(μ₂, η²-HCCR)] (R=FeCp₂ 10, CH₂OH 11), respectively. All clusters were characterized by element analysis, IR and ¹H-NMR spectroscopy.     

Structural tuning of coordination polymers by 4-connecting metal node and secondary building process

Due to variation in ligand's conformation, metal node's connecting geometry, and secondary building process by anions, bat-like, dumbell-like, diamondoid, or pillar-layer topologies are achieved.