Effect of the X and Y substituents on the carbonyl bond in 4-YC<Subscript>6</Subscript>H<Subscript>4</Subscript>C(O)X compounds

Mechanistic aspects of the effect of the X and Y substituents (X = Me, H, CF₃, CN, Br, Cl, F, OH, NH₂; Y = H, NMe₂, NH₂, CN, NO₂) on the carbonyl bond in 4-YC₆H₄C(O)X compounds are discussed on the basis of the ¹³C and ¹⁷O NMR data.     

Cyclische Diazastannylene. XXXII. Zur Synthese und Reaktivität difunktionalisierter Cyclosilagermadiazane—Bildung von Digermanen

Cyclic Diazastannylenes. XXXII. On the Synthesis and Reactivity of Difunctional Cyclosilagermadiazanes—Formation of Digermanes The cyclic bisaminostannylene Me₂Si(t-BuN)₂Sn 1 reacts with tetrahalides of germanium GeX₄(X = Cl, Br, I) forming the bisaminodihalogengermanes 2a, 2b and 2c. The halogen atoms of the compounds 2 may be substituted by alkyl-, amino- and pseudohalide groups: Me₂Si(t-BuN)₂GeXY (X = Y = N₃ 3 ; X = Br, Y = Me 4 , Y = t-Bu 6 , Y = N(SiMe₃)₂ 8a , Y = NEt₂ 9 ; X = Me, Y = N₃ 5a , Y = CN 5b ; X = N₃, Y = t-Bu 7 , Y = N(SiMe₃)₂ 10 ; X = I, Y = N(SiMe₃)₂ 8b ). Reduction of the compounds 2b and 4 with sodium naphthalide generates the digermanes (Me₂Si(t-BuN)₂GeR)₂ (with R = Br 11 , R = Me 12 ) Compound 8b crystallizes in the monoclinic space group P2₁/c with Z = 8 and lattice constants a = 16.205(8), b = 19.854(9), c = 17.537(9) Å, β = 107.50(9)°. Compound 11 crystallizes in the triclinic space group P1 with Z = 2 and lattice constants a = 8.921(4), b = 11.091(5), c = 17.590(8) Å, α = 80.5(1), β = 89.2(1), γ = 71.4(1)°.     

Synthesis,X-ray characterization,and in vitro biological approach of dimeric and polymeric mercury(II) complexes with α-keto stabilized sulfur ylide

Abstract

Reaction of α-keto stabilized sulfur ylide (Me)₂SCHC(O)C₆H₄-p-CN (Y) with HgX₂ (X?=?Cl, Br, and I) led to the formation of new dinuclear products of the type [HgX₂(Y)]₂ (X?=?Cl (1), Br (2), and I (3)). Furthermore, the reaction of the corresponding sulfur ylide (Y) with Hg(NO₃)₂·H₂O in equimolar ratio, using methanol as a solvent, was shown to produce the polynuclear complex [(Y)Hg(NO₃)₂]_n (4). The obtained compounds were characterized using elemental analysis, IR, ¹H and ¹³C NMR techniques. The structures of compounds Y and 1 were characterized by single-crystal X-ray diffraction (XRD) analysis. Also, in order to confirm the crystalline nature of complexes 1–3, powder XRD pattern was used. Likewise, the antioxidant property of the complexes was examined by 1,1-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging which revealed the strong-to-moderate radical scavenging ability (IC₅₀; 0.163?±?0.004 to 0.936?±?0.012?mg·mL^?1) of the synthesized compounds. Further, results from this study indicated that the compounds possess moderate antibacterial activity.     

Mass spectral correlations of halogenated 1,1,1,3,3,3-hexafluoropropanes and 1,1,1-trifluoroethanes

The mass spectral fragmentation patterns at 20 eV of twelve compounds of the type CF₃CXYCF₃ (X, Y =F, Cl, Br, I, H) and five compounds of the type CF₃ CX₂ Y (X, Y= F, Cl, Br) were analyzed. It was noted that the frequency of carbon–helogen and carbon–carbon bond cleavage was quite dependent on the substituents X and Y.     

Synthesis of Mixed Thiuram Disulfides

Abstract

Tris(aminomethyl)phosphines and their oxides form triacidic salts that, unlike the free bases, are air-stable and non-hygroscopic. The salts of the unsubstituted compounds, (NH₃ ⁺CH₂)₃ P(O)_n 3X^?(3b: n = O, X = Br; 4a-c: n = 1, X = Cl, Br, or I), may be prepared directly from 1,3,5-triaza-7-phosphaadamantane (1) or its oxide (2) or from tris(N-carbomethoxylaminomethyl)phosphine oxide (9) by hydrolysis with the appropriate acid. The behaviour of the compounds towards acids and nucleophilic reagents is discussed.     

Transition metal salts of quinoline: synthesis,structure and magnetic behavior of (QuinH)2[MX4]·2H2O [Quin = quinoline; M = Mn,Co, Cu,Zn], (QuinH)2[MnBr2(H2O)2](Br)2 and (QuinH)[Cu(Quin)Br3]

Abstract

A family of compounds of general formula (QuinH)₂MX₄·2H₂O has been prepared and characterized [Quin?=?quinoline; M, X?=?Co,Cl (1); M, X?=?Co,Br (2); M, X?=?Zn,Br (3); M, X?=?Mn,Cl (4)]. The complexes crystallize in the monoclinic space group C2/c as well-isolated layers containing the MX₄^?2 anions and water molecules, separated by the quinolinium cations. The bromide analogue of 4, compound 5 (QuinH)₂[MnBr₂(H₂O)₂](Br)₂, also crystallizes in the C2/c space group, but comprises a co-crystal of manganese bromide dihydrate and quinolinium bromide. The temperature dependent magnetic properties of the complexes are described, along with the tetrachlorocuprate analogue (7). All compounds show weak antiferromagnetic interactions (J/k_B?～?0.06–1.4 K) and good one- or two-dimensional isolation. In addition, the crystal structure of the mixed quinoline/quinolinium complex (QuinH)[Cu(Quin)Br₃] (triclinic, P-1) is reported.     

Synthesis,characterization, and structures of 1-(9-Fluorenyl)-germatrane and 1-(Phenylacetylenyl)germatrane

Syntheses of the title compounds, viz. N(CH₂CH₂O)₃GeY ( 2 Y?Fluorenyl; 4 Y?PhC?C) by the reaction of X₃GeY ( 1 Y?Fluorenyl, X?Br; 5 Y?PhC?C, X?Cl) with N(CH₂CH₂OSnR₃)₃ ( 3 R?Et; 6 R?Bu) are reported including the preparation of the new compound 1 . Identity and structures were established by elemental analyses, ¹H and ¹³C NMR spectroscopy. 2 and 4 were characterized by mass spectrometry. Single crystal structures of 1 , 2 and 4 were determined by X-ray diffraction methods.     

Binuclear cyclopalladated compounds with antitubercular activity: synthesis and characterization of [{Pd(C2,N-dmba)(X)}2(μ-bpp)] (X = Cl,Br, NCO,N3; bpp = 1,3-bis(4-pyridyl)propane)

Reactions between [Pd(C²,N-dmba)(μ-X)]₂ (Hdmba?=?N,N-dimethylbenzylamine; X?=?Cl, Br, NCO, N₃) and 1,3-bis(4-pyridyl)propane (bpp) in 1?:?1 molar ratio at room temperature resulted in the binuclear compounds [{Pd(C²,N-dmba)(X)}₂(μ-bpp)] (X?=?Cl (1), Br (2), NCO (3), N₃ (4)), which were characterized by elemental analyses, infrared (IR), ¹H- and ¹³C{¹H}-NMR spectroscopies, and thermogravimetric analysis. The IR and NMR data of 1–4 were consistent with the presence of bridging bpp. The thermal stability order of the complexes was 4?>?3?>?2?>?1. Compounds 1–4 and bpp were tested against Mycobacterium tuberculosis and their MIC values were determined.     

Synthese,Struktur und Eigenschaften von [nacnac]MX3‐Verbindungen (M = Ge,Sn; X = Cl,Br, I)

Synthesis, Structure, and Properties of [nacnac]MX₃ Compounds (M = Ge, Sn; X = Cl, Br, I) Reactions of [nacnac]Li [(2,6‐ⁱPr₂C₆H₃)NC(Me)C(H)C(Me)N(2,6‐ⁱPr₂C₆H₃)]Li ( 1 ) with SnX₄ (X = Cl, Br, I) and GeCl₄ in Et₂O resulted in metallacyclic compounds with different structural moieties. In the [nacnac]SnX₃ compounds (X = Cl 2 , Br 3 , I 4 ) the tin atom is five coordinated and part of a six‐membered ring. The Sn–N‐bond length of 3 is 2.163(4) Å and 2.176(5) Å of 4 . The five coordinated germanium of the [nacnac]GeCl₃ compound 5 shows in addition to the three chlorine atoms further bonds to a carbon and to a nitrogen atom. In contrast to the known compounds with the [nacnac] ligand the afore mentioned reaction creates a carbon–metal‐bond (1.971(3) Å) forming a four‐membered ring. The Ge–N bond length (2.419(2) Å) indicates the formation of a weakly coordinating bond.     

2-Chloro-3-fluoropyridine copper(II) complexes and the effect of structural changes on magnetic behavior

Abstract

A family of copper(II) compounds has been prepared with the general formula (2-chloro-3-fluoro-pyridine)₂CuX₂·n(Y), where X?=?Cl, Br, n?=?0,1, and Y?=?methanol or water. For the copper chloride complexes, only solvated structures were obtained (1, X?=?Cl, Y?=?H₂O; 2, X?=?Cl, Y?=?CH₃OH) while for the copper bromide compounds, both a desolvated structure and the methanol solvate were prepared (3, X?=?Br, Y?=?none; 4, X?=?Br, Y?=?CH₃OH). Each compound has been characterized by IR, powder X-ray diffraction, single-crystal X-ray diffraction, and temperature-dependent magnetic susceptibility measurement. Compounds 1 and 4 are isostructural, in the space group Cm, and neither exhibits significant magnetic exchange although superexchange pathways are present. Compound 2 also crystallizes in the Cm space group and exhibits weak ferromagnetic interactions (J/k_B?=?1.72(2) K from the 1D-ferromagnetic chain model) which are likely propagated by hydrogen bonding. Compound 3 crystallizes in the space group P2₁/n with the Cu(II) ion sitting on a crystallographic inversion center. Compound 3 exhibits weak antiferromagnetic exchange via two-halide superexchange typical for similar complexes. The magnetic data for 3 were fit to the 1D-antiferromagnetic chain model resulting in J/k_B?=??1.21(1).     

Density functional theory study on the reactions of X− with CH3SY (X,Y = F,Cl, Br,I)

Gas‐phase anionic reactions X^? + CH₃SY (X, Y = F, Cl, Br, I) have been investigated at the level of B3LYP/6‐311+G (2df,p). Results show that the potential energy surface (PES) of gas‐phase reactions X^? + CH₃SY (X, Y = Cl, Br, I) has a quadruple‐well structure, indicating an addition–elimination (A–E) pathway. The fluorine behaves differently in many respects from the other halogens and the reactions F^? + CH₃SY (Y = F, Cl, Br, I) correspond to deprotonation instead of substitution. The gas‐phase reactions X^? + CH₃SF (X = Cl, Br, I), however, follow an A–E pathway other than the last two out going steps (COM2 and PR) that proceeds via a deprotonation. The polarizable continuum model (PCM) has been used to evaluate the solvent effects on the energetics of the reactions X^? + CH₃SY (X, Y = Cl, Br, I). The PES is predicted to be unimodal in the solvents of high polarity. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

CuClS0.94Te1.06 und CuBrS0.92Te1.08, zwei neue Kupfer(I)-chalkogenhalogenide mit neutralen [STe]-Schrauben

CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08, Two New Copper(I) Chalcogen Halides Containing Neutral [STe] Screws CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P2₁/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) ų (CuClS_0.94Te_1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) ų (CuBrS_0.92Te_1.08), both with Z = 4. The crystal structures are dominated by ordered [STe^±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS_0.94Te_1.06) and 336 °C (CuBrS_0.92Te_1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.     

Halomethylated polysulfone: Reactive intermediates to neutral and ionic film-forming polymers

Halomethylation of polysulfone (PS) with C₈H₁₇OCH₂X (X = Cl, Br) in the presence of SnX₄ (X = Cl, Br) led to PS–CH₂X (X = Cl or Br or both) (Scheme 1). Under controlled conditions, PS–CH₂X could be isolated and retains the good film forming properties of PS itself. Interhalogen exchange reactions occur in the presence of SnX₄ (X = Cl, Br) under anhydrous conditions (Scheme 1), or a quaternary ammonium phase transfer catalyst R^*R₃N⁺X^?, under aqueous conditions (Scheme 2). The exchange reactions with R^*R₃N⁺X^?, are favored when R = C₈? C₁₀, and with R = C₄ only if n-octanol is added; otherwise gelation occurs. Exchange in CHCl₃ is attributed to dehydrohalogenation (and generation of dichlorocarbene) of the solvent in the presence of tetrabutyl ammonium hydroxide. Further chemical modifications of PS–CH₂X by reaction with strong nucleophiles, led to hydroxymethyl polysulfone, acetoxymethyl polysulfone, and t-butyl-oxymethyl polysulfone (Scheme 3). Hydroxymethyl polysulfone sometimes gels under basic hydrolytic conditions and is best obtained by methanolysis of PS–CH₂-OAc. Both PS? CH₂? OAc and PS? CH₂O-t-Bu are very stable, and provide a way to generate PS? CH₂Br on need by cleavage with HBr in acetic acid. Direct oxidations with DMSO or tetrabutyl ammonium dichromate (Scheme 4) or indirect oxidations (Scheme 5) produce polysulfone with pendent CHO, CO₂R and PO₃R groups. Finally, polysulfones with linker arms including, carboxy alkyl, hexaglycol or sulfonamido crowns are described (Scheme 6). The reaction products were characterized by ¹H- and ¹³C-NMR. Double irradiation experiments, proved unequivocally, that the first substitution occurred on the B ring of the bisphenol A moiety (see Table I); the second substitution occurs on the A ring in position a. Thermogravimetric analysis generally shows for all modified polysulfones an extra transition at a lower temperature. The area of this band agrees generally with the values expected from calculated substitution degrees.     

Ruthenium(II)-Phthalocyaninate(2–): Darstellung und Eigenschaften von Acido(carbonyl)phthalocyaninato(2–)ruthenat(II), [Ru(X)(CO)Pc2−]− (X = Cl,Br, I,NCO, NCS,N3)

Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) (ⁿBu₄N)[Ru(OH)₂Pc^2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H₂O)(CO)Pc^2?], which yields in tetrahydrofurane with excess (ⁿBu₄N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) isolated as red-violet, diamagnetic (ⁿBu₄N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc^2? ligand at approximately 15100 (B), 28300 (Q₁) und 33500 cm^?1 (Q₂), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N₃, NCO) 1948 cm^?1 (NCS), v(C? N) at 2208 cm^?1 (NCO), 2093 cm^?1 (NCS) and v(N? N) at 2030 cm^?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N₃), 504 (I), 499 (NCO), 498 cm^?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N₃), 336 (NCO) and 224 cm^?1 (NCS). Only v(Ru? I) is RR-enhanced.     

Synthesis and Characterization of 2-Mercapto-1-cyclohexylimidazole–Based Zinc(II) and Cadmium(II) Bromide Complexes: The Crystal Structure of [Zn(Hmim chexyl )2(Br)2] with N–H…Br Intermolecular Hydrogen Bonding Interactions

Reactions of the ligand 2-mercapto-1-cyclohexylimidazole (Hmim^chexyl) with both zinc(II) and cadmium(II) bromides in ethanol solutions afforded 2:1 complexes of the type [M(Hmim^chexyl)₂(Br)₂] (M = Zn 1, and Cd 2) with an MBr₂S₂ configurations. Spectroscopic evidence (FT-IR and ¹H-¹³C NMR) confirms that the exocyclic thione sulfur atoms are the donors in both complexes. Complex 1 crystallizes in a monoclinic system, space group C2/c, a = 16.180(3), b = 10.817(5), c = 13.602(3); α = 90, β = 106.754(17), γ = 90; Z = 4; R1 = 0.0229, wR2 = 0.0554. The coordination geometry about the zinc(II) atom is distorted tetrahedral with average Zn-S and Zn-Br bond lengths of 3.3418(8) and 2.4017(6) Å, respectively. The bromide ions form intermolecular N–H…Br hydrogen bonding with the thione NH groups of the ligand molecule.     

Hydrothermalsynthese und Kristallstruktur der Münzmetall‐Quecksilber‐Chalkogenidhalogenide CuHgSeBr,AgHgSBr und AgHgSI

Hydrothermal Synthesis and Crystal Structure of the Coinage Metal Mercury Chalcogenide Halides CuHgSeBr, AgHgSBr, and AgHgSI The hydrothermal reaction of CuBr and HgSe in concentrated aqueous HBr as solvent at 285 °C yields red crystals of CuHgSeBr, the hydrothermal reaction of AgX (X = Br, I) and HgS in half‐concentrated aqueous HX (X = Br, I) as solvent at 300/400 °C yields yellow crystals of AgHgSBr and AgHgSI. The compounds crystallize isotypically (orthorhombic, Pmma, a = 1020.1(3) pm, b = 431.2(1) pm, c = 925.6(3) pm for CuHgSeBr, a = 964.8(8) pm, b = 466.1(4) pm, c = 942.6(6) pm for AgHgSBr und a = 1015.9(2) pm, b = 464.77(5) pm, c = 984.9(2) pm for AgHgSI, Z = 4). The structures consist of plane folded Hg–Y chains connected by pairs of distorted Y₂X₂ terahedra sharing the X–X‐edge (M = Cu, Ag; X = Br, I; Y = S, Se). Atoms of the monovalent metals M have a strongly distorted tetrahedral coordination of two halogen and two chalcogen atoms. The new structure type shows distinct differences in the arrangement of the Hg–Y chains in comparision to the already known CuHgSeCl, but represents the superposition structure of the order‐disorder phase γ‐Hg₃S₂Cl₂.     

Organometallated Halonium Salts of the Type [{Cp(CO)2Fe}2X]SbY6 (X = Cl,Br, I; Y = F,Cl)

The reaction of CpFe(CO)₂X (X = Cl, Br, I) with SbY₅ (Y = F, Cl) in toluene leads to the cationic, halogen‐bridged compounds [{Cp(CO)₂Fe}₂X]SbY₆ ( 1 – 6 ). The halide of CpFe(CO)₂X is eliminated by the Lewis acid SbY₅, and the fragment “CpFe(CO)₂⁺” reacts with further CpFe(CO)₂X to form the halogen bridge between both the organometallic substituents. The exclusive formation of the counter anion SbY₆^– is caused by the oxidizing action of the antimony pentahalides, by which SbY₃ and the interhalogens XY are always obtained. The compounds have been characterized by their NMR‐, IR‐ and Mass spectra, the compounds 1 – 3 and 6 additionally by single crystal structure analyses. They show decreasing bond angles Fe–X–Fe following the range Cl → Br → I and the VSEPR concept; the two CpFe(CO)₂ groups are staggered with the dihedral angle Cp(centre)–Fe–Fe–Cp(centre) of about 160°.     

1H-, 13C-UND 31P-NMR-SPEKTROSKOPISCHE UNTERSUCHUNGEN AN BIS-(DIALKOXYTHIOPHOSPHORYL)-UND-(DIALKOXYPHOSPHORYL)-SULFANEN UND-POLYSULFANEN

Abstract

Compounds of the following structure

(R¹O)₂(X)P[sbnd]Y–P(X)(OR²)₂

(X = O, Y = S_n (n = 1–4), R¹ = R² = Me, iPr;

X = S, Y = S_n (n = 1–4), R¹, R² = Me, Et, iPr, iBu;

X = S, Y = S-Se-S, S-Te-S, R¹ = R² = Me

were prepared and their NMR spectra were analysed. Depending on the number of sulfur atoms, bonded between the phosphorus atoms, typical ranges of the P-P coupling constants were found for the different sulfanes investigated: ²J_PP from-10 to-20 Hz, ³J_PP less than 3 Hz, ⁴J_PP from +10 to +13 Hz and ⁵J_PP less than 1 Hz. For the small vicinal coupling constants and the relatively large values of ⁴J_PP different possibilities of their interpretation are given.     

Synthesis and reactivity of ω-haloalkyltin compounds

ω-Haloalkyltin trihalides, X(CH₂)_nSnX₃ (n ≧ 3; X = halogen) can readily be prepared in high yields by the direct reaction of stannous halides with α,ω-dihaloalkanes, catalysed by trialkylantimony compounds. The compounds are versatile starting materials for the synthesis of a variety of ω-functionallysubstituted organotin compounds R_3-mX_mSn(CH₂)_n Y (R = alkyl, phenyl; m = 0-3; X = Cl, Br, O; Y = Br, NMe₂, NEt₂, COOH, CHOHR, R₃Sn). ¹H-NMR spectral data for a series of such compounds are presented. The trends observed in the chemical shifts and the ¹¹⁹Sn—methyl proton coupling constants of Me_3-m Br_mSn(CH₂)_nBr (m = 0-3; n = 3-5) are discussed in terms of inductive effects. Intramolecular coordination between the ω-bromine atom and tin could not be demonstrated.     

Strukturen von neuen Bis(pentafluorophenyl)halogenomercuraten [{Hg(C6F5)2}3(μ‐X)]— (X = Cl,Br, I)

Structures of New Bis(pentafluorophenyl)halogeno Mercurates [{Hg(C₆F₅)₂}₃(μ‐X)]^— (X = Cl, Br, I) From the reactions of [PNP]Cl or [PPh₄]Y (Y = Br, I) with Hg(C₆F₅)₂ crystals of the composition [Cat][{Hg(C₆F₅)₂}₃X] (Cat = PNP, X = Cl ( 1 ); Cat = PPh₄, X = Br ( 2 ), I ( 3 )) are formed. 1 crystallizes in the triclinic space group P1¯, 2 and 3 crystallize isotypically in the monoclinic space group C2/c. In the crystals the halide anions are surrounded by three Hg(C₆F₅)₂ molecules. The reaction of [PPh₄]Br with Hg(C₆F₅)₂ under slightly changed conditions gives the compound [PPh₄]₂[{Hg(C₆F₅)₂}₃(μ‐Br)][{Hg(C₆F₅)₂}₂(μ‐Br)] ( 4 ).