Inclusion of thiazyl radicals in porous crystalline materials

The incorporation of benzodithiazolyl (BDTA) and methylbenzodithiazolyl (MBDTA) radicals into porous hybrid frameworks via gas phase diffusion revealed that inclusion appeared selective for the MIL53(Al) framework against a range of other potential hosts. Both PXRD and EPR studies are consistent with retention of a π*-π* dimer motif for BDTA in MIL53(Al)@BDTA whereas MBDTA in MIL53(Al)@MBDTA appears to be monomeric. The guests are readily released by the addition of solvent (CH(2)Cl(2)).     

Reactions of chlorine monofluoride with tetrasulphur tetranitride,thiazyl chloride and thiazyl fluoride

Chlorine monofluoride reacts with tetrasulphur tetranitride to give thiazyl chloride (monomer and trimer) and thiazyl fluoride; with further ClF, NSCl reacts to form NSF then ClNSF₂, and finally N₂, Cl₂ and SF₄. The reaction NSCl/ClF to give NSF/Cl₂ reverses in SO₂ solvent due to removal of ClF as SO₂ClF. NSF was prepared, in a new method, by passing NSCl through a column of CsF at 110°.     

Metal phosphinohydrazone complexes

Russian Chemical Bulletin - The reaction of benzophenone hydrazone with chlorodiphenylphosphine in the presence of triethylamine affords the monophosphino derivative Ph2C=N-N(H)PPh2(1). The...     

Metal complexes of tetramethylethylenediaminetetraacetate

Summary A number of metal complexes of the ligand tetramethylethylenediaminetetraacetate [Edta(OMe)₄ = L] have been characterised. The complexes may be formulated MLCl₂ · xH₂O where M²⁺ = Mn^II, Fe^II, Co^II, Ni^II, Cu^II, Cd^II, Hg^II and Sn^II. I.r., conductivity, magnetic susceptibility and electronic spectral data are discussed.     

Metal complexes of ethylenediaminetetraacetamide

Summary A convenient synthesis of the ligand ethylenediaminetetraacetamide (L) is described, and a number of metal complexes of the general formula MLCl_n · xH₂O (Mⁿ⁺=Ca^II, Mn^II, Fe^II, Co^II, N^II, Cu^II, Zn^II, Mg^II, Ba^II, Cd^II, Hg^II and La^III) prepared. The deprotonated Cu(L-H)₂ · 2 H₂O complex has been characterised and the associated pK values determined. I.r., conductivity, magnetic susceptibility and electronic spectral data are discussed.     

Metal complexes with tropolones

A review of the analytical applications of tropolone and its derivatives.     

Metal complexes of 2-mercaptobenzothiazole

Summary Metal complexes of 2-mercaptobenzothiazole (LH) have been prepared and investigated. The metal complexes obtained were of the types ML₂ (M = Ni, Pd, Pt, Zn, Cd), CuL.LH, and AgL. The copper complex has been shown to contain copper(I). Evidence from the i.r. spectra shows that in all the complexes the ligand is coordinatedvia the thiazole nitrogen and the exocyclic sulfur atom. Adducts of both the nickel and cadmium complexes were obtained with several nitrogen heterocycles. The complex CdL₂py₂ (py = pyridine) is isostructural with the six-coordinate NiL₂py₂ and CoL₂py₂ which possess acis configuration.     

Metal complexes of 1-methyltetrabenzooctadehydrocorrin

In reaction of 2,3-dihydro-3-[(1-hydroxy-1-methyl-1H-isoindol-3-yl)methylene]-1H-isoindol-1-one with hydrazine hydrate in the presence of a template agent (metal acetates) in butanol environment metal complexes formed of 1-methyltetrabenzooctadehydrocorrin. A scheme of formation of these compounds was suggested and their spectral characteristics were investigated.     

Metal complexes of fenoterol drug

Metal complexes of fenoterol (FEN) drug are prepared and characterized based on elemental analyses, IR, ¹H NMR, magnetic moment, molar conductance, and thermal analyses (TG and DTA) techniques. From the elemental analyses data, the complexes are formed in 1:2 [Metal]:[FEN] ratio and they are proposed to have the general formula [Cu(FEN)₂]·2H₂O; [M(FEN)₂(H₂O)₂]·yH₂O (where M = Mn(II) (y = 2), Co(II) (y = 4), Ni(II) (y = 4), and Zn(II) (y = 0) and [Cr(FEN)₂(H₂O)₂]Cl·H₂O. The molar conductance data reveal that all the metal chelates are non-electrolytes except Cr(III) complex, having 1:1 electrolyte. IR spectra show that FEN is coordinated to the metal ions in a uninegative bidentate manner with ON donor sites of the aliphatic –OH and secondary amine –NH. From the magnetic moment measurements, it is found that the geometrical structures of these complexes are octahedral (Cr(III), Mn(II), Co(II), Ni(II), and Zn(II)) and square planar (Cu(II)). The thermal behavior of these chelates is studied using thermogravimetric and differential thermal analyses (TG and DTA) techniques. The results obtained show that the hydrated complexes lose water molecules of hydration followed immediately by decomposition of the coordinated water and ligand molecules in the successive unseparate steps. The FEN drug, in comparison to its metal complexes is also screened for their antibacterial activity against bacterial species (Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Salmonella typhi), Yeasts (Candida albicans and Saccharomyces cervisiae), and Fungi (Aspergillus niger and Aspergillus flavus). The activity data show that the metal complexes have antibacterial activity like that of the parent FEN drug against one or more species.     

Metal complexes of 6-chloropurine

Summary Five Cu(II), Pd(II), Cd(II), Pt(IV), and Au(III) complexes of 6-chloropurine have been obtained. The complexes were characterized by elemental analysis, IR,¹H-NMR and¹³C-NMR spectroscopy. On the basis of these data the structure of the complexes and the coordination of the ligand have been proposed. Thus, the physical and chemical methods supported evidence that in acidic medium, with exception of the Cu(II) complex, 6-chloropurine acts in the monoprotonated form neutralizing the charge of [PdCl₄]^2–, [CdCl₄]^2–, [AuCl₄]^– and [PtCl₆]^2– anions. The thermal behaviour of the complexes has also been studied.

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Metallkomplexe von 6-Chlorpurin

Zusammenfassung Es wurden fünf Komplexe von 6-Chlorpurin mit Cu(II), Pd(II), Cd(II), Pt(IV) und Au(III) erhalten. Die Komplexe wurden mittels Elementaranalysen, IR,¹H-NMR und¹³C-NMR charakterisiert. Auf der Basis dieser Daten wurde eine Komplexstruktur und eine bestimmte Koordination der Liganden vorgeschlagen. Physikalische und chemische Methoden beweisen, daß im sauren Bereich [mit der Ausnahme von Cu(II)] das 6-Chlorpurin in der monoprotonierten Form koordiniert, wobei die Ladung von [PdCl₄]^2–, [CdCl₄]^2–, [AuCl₄]^– und [PtCl₆]^2– jeweils neutralisiert wird. Das thermische Verhalten der Komplexe wurde ebenfalls untersucht.

     

Long-lived π-cation radicals of bilindionato zinc complexes

The title compounds have been prepared by I₂-oxidation in benzene-pyridine solutions and characterized by uv-vis and esr spectroscopy.     

Structure and bonding in simple thiazyl compounds

The molcules NSF, NSO⁻, NSCl, HNSF⁺, HNSO, CH₃NSF⁺, CH₃NSO are investigated at the SCF level and partly with inclusion of electron correlation effects. Equilibrium geometries and relative stabilities of isomers and conformers are reported. Structure constants and relative energies are discussed in connection with the molecular electronic structure as characterized by the results of population analyses.     

Reactions of free radicals with η-allylpalladium(II) complexes: cyclohexyl radicals

Allyl palladium complexes of the types [(η³-allyl)PdCl]₂, (η³-allyl)PdCl(PPh₃) and [(η³-allyl)Pd(PPh₃)₂]Cl (allyl=C₃H₅, 1-MeC₃H₄, 2-MeC₃H₄, 1-PhC₃H₄, 2-PhC₃H₄) react with cyclohexyl radicals derived from the visible light photolysis of (c-hex)Co(DMG)₂(py). The reactions proceed via initial attack of the free radical at the metal center, followed by β-hydrogen elimination and subsequent reductive elimination of propene, 1-butene, isobutene, 3-phenylpropene and 2-phenylpropene, respectively. The 3-phenylpropene can be catalytically isomerized to the thermodynamically more stable 1-phenylpropene by either palladium metal or palladium(0) products, but the formation of 1-butene and 3-phenylpropene as primary products is unusual. A mechanism, differing in many ways from that proposed previously for analogous reactions of phenyl and trityl radicals, is proposed for the overall reaction and supported by use of the labeled cobaloxime, (2,2,6,6-D₄-c-hex)Co(DMG)₂(py).