Gas-phase on-line generation and infrared spectroscopic investigations of polyphosphazenes, (NPX2)3 where X=F, Cl and Br

Gas-phase infrared spectra of polyphosphazenes (phosphonitrilic halides trimer), (NPX2)3 where X=F, Cl and Br have been recorded. The molecules were generated for the first time by an on-line process using solid (NPCl2)3 as a precursor passed over heated sodium fluoride and potassium bromide at about 550 and 700 degrees C for (NPF2)3 and (NPBr2)3 production, respectively. The products were characterized by the infrared spectra of their vapors. The low-resolution gas-phase Fourier transform infrared spectra reported for the first time show strong bands centered at 1295, 1215 and 1200 cm-1, assigned to nu7(E'), in plane PN stretching mode of (NPX2)3, where X=F, Cl and Br, respectively.     

Synthesis and characterization of platinum(II) and (IV) complexes containing hexamethyleneimine ligand: crystal structure of [Pt(hexamethyleneimine)2(cyclobutanedicarboxylato)]·H2O

A series of new platinum(II) and platinum(IV) complexes of the type [Pt^II(HMI)₂X] (where HMI=hexamethyleneimine, X=dichloro, sulfato, 1,1-cyclobutanedicarboxylato [CBDCA], oxalato, methylmalonato, or tatronato) and [Pt^IV(HMI)₂Y₂Cl₂] (where Y=hydroxo, acetato, or chloro) were synthesized and characterized by infrared (IR) spectroscopy, ¹³C and ¹⁹⁵Pt nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Among the complexes synthesized, [Pt^II(hexamethyleneimine)₂(1,1-cyclobutanedicarboxylato)]·H₂O was examined by single-crystal X-ray diffraction. The slightly distorted square planar coordination environment of the platinum metal includes the amino group of the hexamethyleneimine (HMI) molecule and the oxygen atoms of the carboxylato ligand. The cyclobutanedicarboxylic acid (CBDCA) molecule adopts six-member chelating rings with platinum. Hydrogen bonding plays an important part in holding the crystal lattice together.     

Oxidations with alkaline permanganate using monovalent thallium for the back-titration: Determination of iodate,iodide and ferrocyanide

Iodate, iodide, iodine and ferrocyanide can be estimated by oxidation with KmnO₄ in alkaline media; the excess is back-titrated with TI⁷. I^- and I₂ are oxidized to IO₄^- in the presence of Ba⁺² ions but only to IO₃^- in absence of such ions. The direct titration of IO₃^-, I^- with KmnO₄ proved valueless.Ferrocyanide is oxidized by KmnO₄ in alkaline solutions and MnO₂ is formed. In the presence of telluric acid and 0.025–0.1 N NaOH satisfactory results are obtained. Reduction of MnO₄^- with ferrocyanide gives MnO₄^-2 and the results are variable, depending on the rate of adding the ferrocyanide.     

Complexation of palladium cyanide with imidazolidine-2-thione and its derivatives

Summary Pd(CN)₂ reacts with imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione(Diaz), 1,3-diazipnane-2-thione (Diap) and their derivatives to yield complexes of stoichiometry [PdL₂(CN)₂] or [PdL(CN)₂] (L = Imt, Diaz or Diap and L = Imt having N-Me, Et or Pr substituents), which were characterized by elemental analysis, i.r., ¹H and ¹³C n.m.r. spectroscopy. Both mono- and bis ligand complexes are thought to be square planar with the monoligand binding to metal via sulphur (bridging) and the bis ligand via the monodentate thione group. The ¹³C enriched Pd(¹³CN)₂ complex was prepared and the ¹³C n.m.r. recorded. The C-2 resonance of ¹³C n.m.r. of Imt, Diaz or Diap complexes of the copper(I), silver(I), gold(I) and palladium(II) were compared.     

Triosmium clusters derived from the reactions of thioureas with dodecacarbonyltriosmium: Crystal structures of [Os3(CO)11{η 1-SC(NMe2)2}], [Os3(CO)9(μ-OH)(μ-OMeOCO){η 1-SC(NMe2)2}] and [(μ-H)Os3(CO)9{μ 3-NHC(S)NH2}]

The reaction of [Os₃(CO)₁₂] with tetramethylthiourea in the presence of a methanolic solution of Me₃NO·2H₂O at 60° yields the compounds [Os₃(CO)₁₁{η ¹-SC(NMe₂)₂}] (1) in 56% yield and [Os₃(CO)₉(μ-OH)(μ-MeOCO){η ¹-SC(NMe₂)₂}] (2) in 10% yield in which the tetramethylthiourea ligand is coordinatedvia the sulfur atom at an equatorial position. Compound2 is a 50 e^? cluster with two metal-metal bonds and the hydroxy and methoxycarbonyl ligands bridging the open metal-metal edge. In contrast, the analogous reaction of [Os₃(CO)₁₂] with thiourea gives the compounts [(μ-H)Os₃(CO)₁₀{μ-NHC(S)NH₂}] (3) in 8% yield and [(μ-H)Os₃(CO)₉{₃-NHC(S)NH₂}] (4) in 30% yield. In3, the thioureato ligand bridges two osmium atomsvia the sulfur atom, whereas in4 in addition to the sulfur bridge, one of the nitrogen atoms of thioureato moiety bonds to the remaining osmium atom. The decacarbonyl compounds 3 can also be obtained in 50% yield from the reaction of [Os₃(CO)₁₀(MeCN)₂] with thiourea at ambient temperature. Compound3 converts to4 (65%) photochemically. Compound1 reacts with PPh₃ and acetonitrile at ambient temperature to give the simple substitution products [Os₃(CO)₁₁(PPh₃)] and [Os₃(CO)₁₁(MeCN)], respectively, while with pyridine, the oxidative addition product [(μ-H)Os₃(CO)₁₀(μ-NC₅H₄] is formed at 80°C. All the new compounds are characterized by IR,¹-H-NMR and elemental analysis together with the X-ray crystal structures of1,2 and4. Compound1 crystallizes in the triclinic space group P $P\bar 1$ with unit cell parametersa = 8.626(3) Å,b = 11.639(3) Å,c = 12.568(3_ Å,α = 84.67(2)°,β = 75.36(2)°,γ = 79.49(3)°,V = 1199(1) ų, andZ = 2. Least-squares refinement of 4585 reflections gave a final agreement factor ofR = 0.0766 (R _w = 0.0823). Compound2 crystallizes in the monoclinic space group P2_1/n with unit cell parametersa = 9.149(5) Å,b = 17.483(5) Å,c = 15.094(4) Å,β = 91.75(2)°,V = 2413(2) ų, andZ = 4. Least-squares refinement of 3632 reflections gave a final agreement factor ofR = 0.0603 (R _w = 0.0802). Compound4 crystallizes in the monoclinic space group C2/c with unit cell parametersa = 13.915(7) Å,b = 14.718(6) Å,c = 17.109(6) Å,β = 100.44(3)°,V = 3446(5) ų, andZ = 8. Least-squares refinement of 2910 reflections gave a final agreement factor ofR = 0.0763 (R _w = 0.0863).     

4‐[3‐(3,4‐Di­methoxy­phenyl)­prop‐2‐enoyl]­phenyl methacryl­ate and 4‐[3‐(2‐bromo­phenyl)­prop‐2‐enoyl]­phenyl methacryl­ate

Chalcones (α,β‐unsaturated ketones) are effective antitumour agents. It has been proved that having halogen or methoxy groups substituted in various positions of the phenyl ring enhances the activity of chalcones many times. The title compounds, C₂₁H₂₀O₅ and C₁₉H₁₅BrO₃, respectively, were chosen for crystallographic study in order to determine their structures and conformations. In both compounds, the keto group is in the s‐cis conformation and is almost planar. There are weak intramolecular interactions in both structures.     

Investigations of regio- and stereoselectivities in the synthesis of cytotoxic isoxazolidines through 1,3-dipolar cycloadditions of nitrones to dipolarophiles bearing an allylic oxygen

Regio- and stereoselectivities in cycloadditions of nitrones to dipolarophiles bearing an allylic oxygen, which furnishes substituted-isoxazolidine analogs of the furanose ring of nucleosides, have been investigated. Although the obtained regioselectivities are anticipated, a rationalization of the preferred formation of endo-cycloadducts necessitates the involvement of an allylic oxygen in secondary interaction. The obtained isoxazolidines display cytotoxic activities against a number of human cancer cell lines.     

R7-binding protein targets the G protein β5/R7-regulator of G protein signaling complex to lipid rafts in neuronal cells and brain

Background  

Heterotrimeric guanine nucleotide-binding regulatory proteins (G proteins), composed of Gα, Gβ, and Gγ subunits, are positioned at the inner face of the plasma membrane and relay signals from activated G protein-coupled cell surface receptors to various signaling pathways. Gβ5 is the most structurally divergent Gβ isoform and forms tight heterodimers with regulator of G protein signalling (RGS) proteins of the R7 subfamily (R7-RGS). The subcellular localization of Gβ 5/R7-RGS protein complexes is regulated by the palmitoylation status of the associated R7-binding protein (R7BP), a recently discovered SNARE-like protein. We investigate here whether R7BP controls the targeting of Gβ5/R7-RGS complexes to lipid rafts, cholesterol-rich membrane microdomains where conventional heterotrimeric G proteins and some effector proteins are concentrated in neurons and brain.     

N‐(Ferrocenecarbonyl)‐N′‐(quinolin‐8‐yl)thio­urea

In the title compound, [Fe(C₅H₅)(C₁₆H₁₂N₃OS)], the 8‐am­inoquinoline and acyl­thio­urea moieties are almost planar. There are two perpendicular arrangements of the mol­ecules in the crystal with slightly different conformations. The two cyclo­penta­dienyl rings in each mol­ecule are parallel and eclipsed.