Zinc(II), cadmium(II) and mercury(II) complexes of 4,6-dimethyl-pyrimidine-2(1H)-one

The following zinc(II), cadmium(II) and mercury(II) complexes of 4,6-dimethylpyrimidine-2(1H)-one (L) have been prepared and investigated by conductometric,IR and Raman methods: MX₂L₂ (M = Zn, X = Cl, Br(CHCl₃, I(CHCl₃, CF₃COO; M = Cd, X = Cl, Br CF₃COO; M = Hg, X = Cl, CF₃COO), Cd₂I₄L₃, Hg₃X₆L₂ (X = Cl, Br), Hg₃X₆L₄(X = Br, I), MX₂L₄·6H₂O (M = Zn, Cd, X = CIO₄, BF₄; M = Hg, X = CIO₄. The ligand is principally bonded through the unprotonated nitrogen atom and in some complexes also through the carbonylic oxygen atom. The zinc halide complexes are tetrahedrally coordinated, the trifluoroacetate ion is coordinated as a monodentate ligand.     

Reactions of xenon difluoride: Oxidative fluorination of methyl derivatives of the p-block elements

A survey has been carried out to determine how xenon difluoride reacts with methyl derivatives of p-block elements, Me_nX (n = 3, X = N, P, As, or Sb; n = 2, X = O, S, or Se; n = 1, X = Cl, Br, or I), on the basis of NMR measurements, tensimetric and IR analysis of the gaseous products, and mass balances. The reaction proceeds smoothly in most cases, although a Freon like CCl₃F may be needed as a moderator; the rate of the reaction seems to reflect the basicity of the substrate Me_nX. The difluoride Me_nXF₂ is formed in the cases where X = P, As, Sb, Se, or I. The scope of xenon difluoride in these conditions as a mild selective oxidative fluorinating agent is illustrated by the synthesis of the known compounds (CF₃)₂XF₂ (X = S or Se) and the novel compound Me(CF₃)SeF₂. By contrast, cleavage of CH bonds, with the formation of CH₂F derivatives, is the predominant path in the cases where X = N, O, or S, and cleavage of CX bonds, with the formation of MeF, occurs in the cases where X = Cl or Br.     

Zinc(II), Cadmium(II), and Mercury(II) Complexes of 2-Methyl-benzoselenazole

The following zinc(II), cadmium(II) and mercury(II) complexes of 2-methyl-benzoselenazole (L) have been prepared and studied by conductometric and i.r. methods: MLX₂ (M ? Cd, Hg, X ? Cl, Br, I), ML_1.5X₂ (M ? Zn, X ? ClO₄(4 H₂O); M ? Hg, X ? NO₃, ClO₄), ML₂X₂ (M ? Zn, X ? Cl, Br, I, NO₃; M ? Cd, X ? NO₃, ClO₄). The ligand is N-bonded. All the anions are coordinated.     

Darstellung und Reaktionen von Selenocarbonyldifluorid und seines cyclischen Dimeren 2,2,4,4-Tetrafluor-1,3-diselenetan [l]

Inhaltsübersicht. Das erstmals hergestellte B(SeCF₃)₃ zerfällt unter dem katalytischen Einfluß von Alkalifluoriden zu F₂C=Se und BF₃. In Anwesenheit von BF₃ polymerisiert F₂CSe bereits. bei ?;80°C. Oberhalb 150°C depolymerisiert (F₂CSe)_n wieder zu F₂C=Se und. Durch Halogenaddition an F₂C = Se gewinnt man F₂XCSeX (X = Cl, Br). Das in der Reihe Cl_3–nF_nCSeCl noch fehlende Cl₂FCSeCl wird durch Umsetzung von CSe₂, ClF und Cl₂ synthetisiert. F_nCl_3–nCSeCl (n = 1. 2) liefert mit Zinn die entsprechenden symmetrischen Diselane, mit AgCN die Selenocyanate. Durch Halogenaustausch mit BX₃ (X = Cl, Br) wird umgewandelt. XC(S)Cl reagiert mit Hg(SeCF₃)₂ zu CF₃SeC(S)X (X = F, Cl. CF₃Se). Daraus werden durch Chloraddition die entsprechenden Sulfenylchloride synthetisiert. IR-NMR- und Massenspektren der neu hergestellten Substanzen werden angegeben. Preparation and Reactions of SeCF₂ and its Cyclic Dimer 2,2,4,4-Tetrafluoro-1,3-diselenetane Abstract. B(SeCF₃)₃, prepared for the first time, decomposes under the influence of alkali metal fluorides to F₂C=Se and BF₃. In presence of BF₃, SeCF₂ polymerizes even at ?80°C. Above 150°C (F₂CSe)n depolymerizes to F₂C = Se and Halogen addition to F₂C=Se produces F₂XCSeX (X = Cl, Br). The compound Cl₂FCSeCl could be synthesized by the reaction of CSe₂ with ClF and Cl₂. These selenenylchlorides react with tin producing the corresponding symmetric diselenides whereas with AgCN the selenocyanates are formed. can be transformed to through halogen exchange reaction with BX₃ (X = Cl, Br). XC(S)Cl reacts with Hg(SeCF₃)₂ to give CF₃SeC(S)X (X = F, Cl. CF₃Se), from which the corresponding sulfenylchlorides can be synthesized by chlorine addition. I.r., n.m.r., and mass spectra of the newly prepared compounds are reported.     

Force field studies of some trifluoromethyl- and trichloromethyl-mercury-II) compounds

Force constants of [Hg(CF₃)₂], [Hg(CCl₃)₂], [Hg(CF₃)X] (X = Cl, Br, or I) and [Hg(CCl₃)X] (X = Cl or Br) have been calculated using a valence force field and wavenumber data from solutions. The potential energy distributions show substantial mixing between the symmetrical stretching and umbrella deformation coordinates of the trihalomethyl groups. The high degree of mixing of HgC and HgX stretching coordinates in [Hg(CF₃)Br] and [Hg(CF₃)I] accounts for the discontinuous frequency and intensity trends in the [Hg(CF₃)X] series.The results are discussed in comparison with methylmercury and other trifluoromethyl systems.     

Preparation,infrared, Raman and N.M.R. spectra of N,N′-Diethylthiourea complexes with zinc(II), cadmium(II) and mercury(II) halides

Several complexes of N,N′-diethylthiourea (Dietu) with zinc(II), cadmium(II) and mercury(II) halides were prepared and characterized by i.r. (4000–60 cm^?1), raman (400–60 cm^?1), in the solid state and n.m.r. and conductometric methods in solution. The complexes Zn(Dietu)₂X₂, Cd(Dietu)₂X₂ (X ? Cl, Br, I) and Hg(Dietu)₂X₂ (X ? Br, I) are tetrahedral species in which intramolecular ? NH …? X interactions have been observed. The 1:1 mercury(II) complexes, Hg(Dietu)X₂ (X ? Cl, Br), appear to have a dimeric tetrahedral halide-bridged structure in the solid state. In all these complexes N,N′-diethylthiourea is sulphur-bonded to the metal.     

Synthesis and Crystal Structure of Copper(II) Trifluoroacetates,Cu2(CF3COO)4 · 2 CH3CN and Cu(CF3COO)2(H2O)4

Cu₂(CF₃COO)₄ · 2 CH₃CN ( I ) and Cu(CF₃COO)₂(H₂O)₄ ( II ) have been prepared by concentrating of acetonitrile and aqueous solutions respectively. According to X-ray data, the complex I consists of binuclear molecules with Cu–O 1.969 Å, Cu–N 2.114 Å. The Cu…Cu distance was found to be 2.766 Å, one of the longest for dimeric structures, apparently, due to the high acidity of trifluoroacetic acid. The coordination environment of Cu atom in II can be described as 4 + 2: 2 Cu–O (H₂O) 1.937 Å, 2 Cu–O (CF₃COO) 1.985 Å, 2 Cu–O (H₂O) 2.447 Å. The mononuclear structure is stabilized by formation of two intra- and six intermolecular hydrogen bonds.     

Reaktive E=C(p‐p)π‐Systeme. 54 [1] Reaktionen des Perfluor‐2‐arsapropens,F3CAs=CF2 (1), mit H‐aciden Verbindungen Me2EH (E = N,P, As) und MeE′H (E′ = O,S, Se)

Reactive E=C(p‐p)π‐Systems. 54 [1] Reactions of perfluoro‐2‐arsapropene, F₃CAs=CF₂ (1), with H‐acidic compounds Me₂EH (E = N, P, As) and MeE′H (E′ = O, S, Se) The reactions of the perfluoro‐2‐arsapropene ( 1 ) with H‐acidic compounds Me₂EH (E = N, P, As) and MeE′H (E′ = O, S, Se), respectively, proceed via addition to the As=C double bond yielding either secondary arsanes F₃C(H)AsCF₂X (X = NMe₂, PMe₂, OMe, SMe) or AsX derivatives (X = AsMe₂, SeMe). Me₂‐AsH is obviously a border case nucleophile because, besides the AsX derivative as main product, small amounts of the arsane are formed indicative for the reverse addition pathway. With the strong base Me₂NH, the addition is followed immediately by HF elimination producing the fairly stable arsaalkene F₃CAs=C(F)NMe₂ ( 4 ) which had already been obtained by reaction of HAs(CF₃)₂ with three equivalents of Me₂NH. The novel rather labile compounds were identified by spectroscopic (NMR, GC/MS) investigations. – Quantum chemical DFT calculations [B3LYP/6‐311+G(d,p)] were carried out to determine the relative energy of the isomeric products and the thermodynamics of the addition reactions.     

Beiträge zur 14/15N-NMR-Spektroskopie CF3S-substituierter Stickstoffverbindungen mit natürlicher Isotopenhäufigkeit

Contributions on ^14/15N-N.M.R. Spectroscopy of CF₃S-substituted Nitrogen Compounds with Natural Isotope Abundance ¹⁴N and ¹⁵N data are reported of compounds of the type CF₃SNXY (X = H, Y = H, SiMe₃; X = Y = SiMe₃), (CF₃S)₂NX (X = H, CH₃, CH₂OH, SiMe₃, SnMe₃), as well as (CF₃S)₃N and [(CF₃S)₂N]₂Hg. The δ-values of the CF₃S-amines lie at higher field than those of the non-fluorinated RSNR₂ compounds. This is attributed to the large s-contribution of the S? N bond (sp² hybridization of the N atom), as a result of the electron withdrawing effect of the CF₃ group. The ? I effect of the CF₃S group on the δ-values is thereby not discernible. The notion of a p_π – d_π interaction between S and N atoms (N acting as a donor) is not supported by the ^14/15N-n.m.r. data. With the aid of known N-n.m.r. data a dependance was found between δ and EN that leads to a straight line, according to which the substituents at N can be divided into two categories with regard to their steric effect. The CF₃S substituted amines show in accord with this straight line a higher field displacement. The known regularities of the δ-values (-α, -β-effect, the influence of hydrogen bridging) are qualitatively valid for the CF₃S amines too. The substitution of Me₃Si groups by CF₃S ones enhances the shielding effect at the N-nucleus; in secondary amines an increasing s-character of the N? H bond is evident from the J_NH value.     

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.     

Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

The reaction of dibenzenediselenide, (SePh)₂, with mercury in refluxing xylene gives bis(benzeneselenolato)mercury(II), [Hg(SePh)₂], in a good yield. (ⁿBu₄N)[Hg(SePh)₃] is obtained by the reaction of [Hg(SePh)₂] with a solution of [SePh]^– and (ⁿBu₄N)Br in ethanol. The solid state structures of both compounds have been determined by X-ray diffraction. The mercury atom in [Hg(SePh)₂] (space group C2, a = 7.428(2), b = 5.670(1), c = 14.796(4) Å, β = 103.60(1)°) is linearly co-ordinated by two selenium atoms (Hg–Se = 2.471(2) Å, Se–Hg–Se = 178.0(3)°). Additional weak interactions between the metal and selenium atoms of neighbouring molecules (Hg…Se = 3.4–3.6 Å) associate the [Hg(SePh)₂] units to layers. The crystal structure of (ⁿBu₄N)[Hg(SePh)₃] (space group P2₁/c, a = 9.741(1), b = 17.334(1), c = 21.785(1) Å, β = 95.27(5)°) consists of discrete complex anions and (ⁿBu₄N)⁺ counter ions. The coordination geometry of mercury is distorted trigonal-planar with Hg–Se distances ranging between 2.5 and 2.6 Å.     

Spectroscopic investigations of CF3Se-derivatives

The vibrational spectra of CF₃SeH, CF₃SeD, CF₃SeCl, CF₃SeBr, CF₃SeCN, CF₃SeCl₃, (CF₃)₂Se and (CF₃Se)₂ are reported, and vibrational assignments presented. N.m.r. parameters for a wide range of CF₃Se-derivatives are tabulated.     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Trifluormethylselenyl-Verbindungen des N,P und As

Trifluoromethylselenyl Compounds of N, P, and As The reaction of CF₃SeBr with NH₃ leads, depending on conditions, to (CF₃Se)_nNH_3?n, where n = 1, 2 or 3. CF₃SNCO reacts with CF₃SeNH₂ to give CF₃SNHCONHSeCF₃, and (CF₃Se)₃N with P(C₆H₅)₃ provides CF₃SeN ?P(C₆H₅)₃. (CF₃Se)₃E (where E = P, As) is formed by the reaction of Hg(SeCF₃)₂ with EBr₃ in CS₂. Analogously, from Hg(SeCF₃)₂ and P₂J₄ in CS₂ (CF₃Se)₂PP(SeCF₃)₂ is obtained that contains (CF₃Se)₃P as a contamination. While reacting C₆H₅PJ₂ or C₆H₅P(J)(J)C₆H₅ with Hg(seCF₃)₂ respectiverly C₆H₅P(SeCF₃)₂ is formed. The latter can be also obtained from (C₆H₅P)₅ and CF₃SeSeCF₃. IR, ¹⁹F, ³¹P, ⁷⁷Se NMR, and MS data are given.     

Perfluoro- ω -iodo-3-oxaalkanesulfonyl fluorides as intermediates for surfactants and vinyl compounds

The well known fluorosulfonyldifluoroacetyl fluoride (I), FOCCF₂SO₂F (I) quantitatively formed from sulfur trioxide and TFE through the tetrafluoroethanesultone has been converted into the octafluoro- -5-iodo-3-oxapentanesulfonyl fluoride (II) ICF₂CF₂OCF₂CF₂SO₂F (II) by the well known reaction (1) involving MF, iodine, TFE in aprotic solvents.The iodo compound (II) allowed us to obtain TFE telomers having both fluorosulfonyl and iodo as terminal groups.The said telomers have been easily converted into surfactants (III) through fluorination and vinyl derivatives (IV) by dehalogenation.CF₃CF₂(CF₂CF₂)_nOCF₂CF₂SO₃M (III)CF₂CF(CF₂CF₂)_nOCF₂CF₂SO₂F (IV)     

Mono‐ and dinuclear CuII complexes of the benzyldipicolylamine (BDPA) ligand: crystal structure,synthesis and characterization

The crystal structures of mono‐ and dinuclear Cu^II trifluoromethanesulfonate (triflate) complexes with benzyldipicolylamine (BDPA) are described. From equimolar amounts of Cu(triflate)₂ and BDPA, a water‐bound Cu^II mononuclear complex, aqua(benzyldipicolylamine‐κ³N ,N′ ,N ′′)bis(trifluoromethanesulfonato‐κO )copper(II) tetrahydrofuran monosolvate, [Cu(CF₃SO₃)₂(C₁₉H₁₉N₃)(H₂O)]·C₄H₈O, (I), and a triflate‐bridged Cu^II dinuclear complex, bis(μ‐trifluoromethanesulfonato‐κ²O :O ′)bis[(benzyldipicolylamine‐κ³N ,N′ ,N ′′)(trifluoromethanesulfonato‐κO )copper(II)], [Cu₂(CF₃SO₃)₄(C₁₉H₁₉N₃)₂], were synthesized. The presence of residual moisture in the reaction medium afforded water‐bound complex (I), whereas dinuclear complex (II) was synthesized from an anhydrous reaction medium. Single‐crystal X‐ray structure analysis reveals that the Cu^II centres adopt slightly distorted octahedral geometries in both complexes. The metal‐bound water molecule in (I) is involved in intermolecular O—H…O hydrogen bonds with triflate ligands and tetrahydrofuran solvent molecules. In (II), weak intermolecular C—H…F(triflate) and C—H…O(triflate) hydrogen bonds stabilize the crystal lattice. Complexes (I) and (II) were also characterized fully using FT–IR and UV–Vis spectroscopy, cyclic voltammetry and elemental analysis.     

Reaktionen an Isocyanidverbindungen

By the reaction of FSO₂N?PCl₃ with perfluorpropionic acid FSO₂NHC(O)C₂F₅ is formed, which yields FSO₂N?C(Cl)? C₂F₅ (I) with PCl₅. The chlorine atom in (I) could be replaced by the substituents NH₂ (II) and N(C₂H₅)₂ (III). FSO₂N?C(Cl)? CF₃ reacts with AgOCN, AgSCN, unhydrous HF and 2,3-dimethylbutadiene. FSO₂N(CH₃)? C(O)F reacts with elemental fluorine under exchange of a proton against a fluorine atom to give FSO₂N(CH₂F)? C(O)F, which liberates at room temperature COF₂ and trimerises to form 1,3,5-Tris-fluorosulfonyl-s-triazine (VIII). The amides FSO₂N?C(CH₃)NH₂ and FSO₂N?C(CF₃)NH₂ react with SF₄ in the presence of NaF to yield the iminosulfur difluorides FSO₂N?C(CH₃)? NSF₂ (IX) and FSO₂N?C(CF₃)? NSF₂ (X)     

Formation of the perfluoro-2,6-dimethyl-2,4,6-triaza-hept-3,4-dienium ion by trimerization of perfluoro-azapropene

The reaction of CF₃NCF₂ with SbF₅, from which previously a cyclotrimer has been obtained, can be directed to selectively yield the acyclic trimeric cation (III) if carried out in SO₂ as a solvent. The derivatives (V) and (VII) were obtained when (III) was treated with F^Θ and (C₂H₅)₂O, respectively, while (VIII) and (IX) were formed by hydrolysis of (III). (VI) was obtained from (V) and BCl₃. All compounds were isolated, characterized analytically and investigated by infrared, Raman, mass and NMR spectroscopy.[(CF₃)₂NCFNCFN(CF₃)₂]⁺ (III) (CF₃)₂NCFNCF₂N(CF₃)₂ (V)(CF₃)₂NCClNCCl₂N(CF₃)₂ (VI) (CF₃)₂NC(OC₂H₅)NCF₂N(CF₃)₂ (VII)(CF₃)₂NCFNCON(CF₃)₂ (VIII) (CF₃)₂NCONH₂ (IX)     

The reaction of boron trihalides with CF3Sn(CH3)3 in the presence of trimethylamine

The reaction of CF₃Sn(CH₃)₃ with BCl₃ and BBr₃ in the presence of trimethylamine has been investigated. The volatile adducts CF₂XBF₂·N(CH₃)₃ (X = F, Cl and Br) have been isolated from the complex reaction mixture while the anions BF^?₄, CF₂XBF^?₃, CF₃BF₂CF₂X^? and (CF₂X)₂BF^?₂ have been identified in the residue. [(CH₃)₃NH][CF₂ClBF₃] has been isolated. The formation of the CF₂XB derivatives is likely to occur via CF₂ insertion, which is promoted by the presence of N(CH₃)₃. NMR, IR, Raman and mass spectra of the novel fluoromethyl borane derivatives are reported.     

Umsetzungen von Thiazylhalogeniden XSN (X = F,Cl) mit perfluorierten Iminen Rf2NH (Rf = F,CF3, CF3S, (CF3)2C, (CF3)2 S): Versuche zur Darstellung von Aminothiazylen (N?SN)

Reactions of Thiazyl Halides XSN (X = F, Cl) with Perfluorinated Imines R_f2 NH (R_f = F, CF₃, CF₃S, (CF₃)₂C?, (CF₃)₂S?): Attempted Preparations of Aminothiazyls (?N? S?N) Thiazyl halides or their precursors Cl₃S₃N₃ and FC(O)N?SF₂ react with perfluoro imines to provide the corresponding aminothiazyls as unstable and reactive intermediates. While with HNF₂ or KF · HNF₂ the final products N₂F₄ and S₄N₄ are formed, [(CF₃)₂N]₂Hg reacts with Cl₃S₃N₃ to give CF₃N?CF₂, FSN, and HgCl₂. The expected product CF₃SN?S?NSCF₃ ( 4 ) is obtained from (CF₃S)₂NH or Hg[N(SCF₃)₂]₂ and FSN probably via (CF₃S)₂ NSN. Surprisingly, (CF₃)₂C?NLi forms with ClSN, Cl₃S₃N₃ or [S₃N₂Cl]Cl in the presence of NH₄Cl 4,5-Dihydro-3,3,5,5-tetrakistrifluoromethyl-3H-1λ⁴,2,4,6-thiatriazine ( 6 ) and (CF₃)₂C?NS_xN?C(CF₃)₂ (X = 1, 2) ( 7a, b ) as byproducts. A CsF catalyzed reaction at 70 to 80°C between (CF₃)₂C?NLi and FSN provides low yields of (CF₃)₂C?N? S? N?S?NCF(CF₃)₂ ( 8 ) together with 7a, b. The latter are the only products without CsF. When (CF₃)₂S?NH is treated with FSN, the compounds CF₃SCF₃, S₄N₄, and N₂ are identified. It is shown by ¹⁹F and ¹⁴N-n.m.r. spectroscopy that (CF₃)S?NSN is an unstable intermediate.