Crystal and molecular structure of nitrosyl(1,10-phenanthroline)-bis(triphenylphosphine)iridium(I) Dihexafluorophosphate, [Ir(NO)(phen)(PPh3)2][PF6]2

Summary The structure of [Ir(NO)(phen)(PPh₃)₂][PF₆]₂ has been determined from x-ray diffractometer data. The compound crystallizes in space groupPnam with four molecules in a unit cell witha = 19.924(12),b = 14.793(9) andc = 16.348(9) A. Full-matrix least-squares refinement has led to a final R value of 0.061 for the 4796 observed reflections. The structure consists of well-separated ions, and the geometry around the metal is trigonal bipyramidal with nitrosyl and bidentate 1,10-phenanthroline (in spite of the very narrow bite angle of 75.8°) ligands occupying the equatorial positions and the triphenylphosphine ligands the axial positions. The cation has an imposed crystallographicm symmetry. Important bond lengths are as follows: Ir-P, 2.391(3): Ir-N (nitrosyl) 1.700(12): Ir-N (1,10-phenanthroline) 2.103(12) and 2.142(11): N-O, 1.201(18)A. The nitrosyl ligand is linear [Ir-N-O = 179.9(9)°] so that this complex can be formulated as an NO⁺ complex of iridium(I).     

A comparative study of several HPLC methods for determining free amino acid profiles in honey

A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results.     

From cyclopentadiene to isoxazoline-carbocyclic nucleosides: a rapid access to biological molecules through nitrosocarbonyl chemistry

A rapid access to carbocyclic nucleosides containing a fused isoxazoline ring is proposed starting from cyclopentadiene. The route involves an hetero Diels-Alder cycloaddition reaction of nitrosocarbonylbenzene followed by a 1,3-dipolar cycloaddition of nitrile oxides, cleavage of the N-O tether and elaboration of the heterocyclic aminols into nucleosides via linear construction of purine and pyrimidine heterocycles.     

Reactions of organomercury fulminates with acetylene derivatives

Organomercury fulminates react with acetylene derivatives to give unstable 3-(organomercurio)isoxazoles, which isomerize to 2-cyanoenolates. These are hydrolyzed with hydrochloric acid to the corresponding enols and are cleaved by water at the double bond. With monosubstituted acetylenes, substitution at the free position by the organomercury residue is predominant.     

Asymmetric zirconocene precursors for catalysis of propylene polymerization

Racemic isopropylidene (1-η⁵-cyclopentadienyl)(1-η⁵-indenyl) dichlorozirconium and the 3-methylindenyl derivative have been synthesized and characterized. These precursors activated with methylaluminoxane produce poly(propylene) with hemiisotactic microstructures. © 1994 John Wiley & Sons, Inc.     

Bis(μ‐acetato‐κ3O,O′:O′)bis[bis(acetato‐κ2O,O′)diaquadysprosium(III)] tetrahydrate

The title compound, [Dy₂(C₂H₃O₂)₆(H₂O)₄]·4H₂O, crystallizes in the form of dimeric units related by an inversion centre. Each cation is nine‐coordinate, binding to two water mol­ecules and three acetate groups, two of which are bidentate and the third tridentate. This last acetate group acts as a bridge between neighbouring metal atoms, leading to an intradimer Dy?Dy separation of 4.170 (1) Å.     

Conductance in homomorphous solvents: Tetrabutylammonium salts and alkali picrates in butyrolactone-sulfolane mixtures

Conductance measurements are reported for LiPi, NaPi, KPi, RbPi, CsPi, Bu₄NPi, Bu₄NBr, Bu₄NClO₄, Bu₄NNO₃, and Bu₄NBBu₄ at 25°C in -butyrolactone-sulfolane mixtures. In these mixtures of solvents that are practically homomorphous, isodielectic and with comparable dipole moments, the ion pair association and ionic mobilities of large ions conform to the expectations of the primitive model. Electrolytes containing lithium or sodium ions show anomalies indicating that other factors besides shape, dipole moment, and polarizability of the solvent molecules are involved in the association and transport processes of these ions.     

Molybdenum(VI) and molybdenum(V) mononuclear and dinuclear complexes with 1,3-diphenyl-1,3-propanedione

Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO₂(LL)₂], [Mo₂O₅(LL)₂], [Mo₂O₄(LL)₂], [MoOCl(LL)₂], [MoCl₂(LL)] and [MoO(OH)(LL)₂)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring.