Unusual monodentate binding mode of 2,2'-dipyridylamine (L) in isomeric trans-(acac)2RuII(L)2, trans-[(acac)2RuIII(L)2]ClO4, and cis-(acac)2RuII(L)2 (acac = acetylacetonate). synthesis, structures, and spectroscopic, electrochemical, and magnetic aspects

The reaction of cis-Ru(acac)2(CH3CN)2 (acac = acetylacetonate) with 2,2'-dipyridylamine (L) in ethanolic medium resulted in facile one-pot synthesis of stable [(acac)2RuIII(L)]ClO4 ([1]ClO4), trans-[(acac)2RuII(L)2] (2), trans-[(acac)2RuIII)L)2]ClO4 ([2]ClO4), and cis-[(acac)2RuII(L)2] (3). The bivalent congener 1 was generated via electrochemical reduction of [1]ClO4. Although in [1]+ the dipyridylamine ligand (L) is bonded to the metal ion in usual bidentate fashion, in 2/[2]+ and 3, the unusual monodentate binding mode of L has been preferentially stabilized. Moreover, in 2/[2]+ and 3, two such monodentate L's have been oriented in the trans- and cis-configurations, respectively. The binding mode of L and the isomeric geometries of the complexes were established by their single-crystal X-ray structures. The redox stability of the Ru(II) state follows the order 1 < 2 < 3. In contrast to the magnetic moment obtained for [1]ClO4, mu = 1.84 muB at 298 K, typical for low-spin Ru(III) species, the compound [2]ClO4 exhibited an anomalous magnetic moment of 2.71 muB at 300 K in the solid state. The variable-temperature magnetic measurements showed a pronounced decrease of the magnetic moment with the temperature, and that dropped to 1.59 muB at 3 K. The experimental data can be fitted satisfactorily using eq 2 that considered nonquenched spin-orbit coupling and Weiss constant in addition to the temperature-independent paramagnetism. [1]ClO4 and [2]ClO4 displayed rhombic and axial EPR spectra, respectively, in both the solid and the solution states at 77 K.     

Organonickel(II) Complexes with Anionic N-Donor Ligands. Hydration of coordinated nitriles at a nickel(II) site

The hydroxo complex (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-OH)₂]reacts with 2,3,4,5,6-pentafluoro benzenamine (C₆F₅-NH₂), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC₆H₄, 4-MeOC₆H₄), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-C₆F₅NH)₂] ( 1 ) and (Bu₄N)₂[{Ni(C₆F₅)₂} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu₄N[Ni(C₆F₅)2(ArN₃Ar)] ( 3 – 5 ), Bu₄N[Ni(C₆F₅)₂(pyNPh)] ( 6 ), and Bu₄N[Ni(C₆F₅)₂(pyCONPh)] ( 7 ). The hydroxo.complex (Bu₄N)₂[{Ni(C₆F₅)2-(μ-OH)}₂] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, ¹H and ¹⁹F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu₄N)₂[{Ni(C₆F₅)₂}₂(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°.     

Fluorimetric determination of the fungicide benomyl after solvolysis

A simple spectrofluorimetric method for the determination of the fungicide benomyl in grapes is described. Benomyl is rapidly solvolysed in organic solvents to give the highly fluorescent metabolite carbendazim. Solvent effects on the spectral shape and their influence on analytical performance are studied. DMF was found to be the best solvent. The method is sensitive to 12 ng/ml benomyl, and has an RSD at the 0.5 g/ml level of 2.2%. The method is suitable for determining benomyl in spiked grapes, with recoveries in the range 97 to 104%.     

Enzymatic desaturation of fatty acids: delta11 desaturase activity on cyclopropane acid probes

The formation of methylenecyclopropanes by enzymatic desaturation of 11-cyclopropylundecanoic acid (1) and its disubstituted derivatives cis- and trans-3-5 has been investigated using the Delta(11) desaturase of Spodoptera littoralis as model enzyme. Gas chromatography coupled to mass spectrometry analyses of methanolyzed lipidic extracts from tissues incubated with each probe revealed that all the cyclopropyl fatty acids were transformed into the corresponding 11-cyclopropylidene acids, except for compound trans-5 (5b), which was not desaturated at C11. The formation of methylenecyclopropane 9 as the only reaction product from 1 indicates that a potential radical intermediate is too short-lived to allow rearrangement reactions. Information on the Delta(11) desaturase substrate binding domain is provided considering the cyclopropyl probes 3-5 as conformationally restricted analogues of the straight-chain substrates.     

Indirect spectrophotometric determination of cyanide

A spectrophotometric method for cyanide based on its inhibition of the colour formation reaction between nickel(II) and 3-(4,5-dimethyl-2-thiazolylazo)-2,6-dihydroxybenzoic acid has been developed, and allows the determination of down to 0.1 g of cyanide. Most of the interferences can be avoided by displacement of the hydrogen cyanide using an arsine generator.     

Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H2

The concept of metal–ligand cooperation opens new avenues for the design of catalytic systems that may offer alternative reactivity patterns to the existing ones. Investigations of this concept with ligands bearing a boron center in their skeleton established mechanistic pathways for the activation of small molecules in which the boron atom usually performs as an electrophile. Here, we show how this electrophilic behavior can be modified by the ligand trans to the boron center, evincing its ambiphilic nature. Treatment of diphosphinoboryl (PBP) nickel–methyl complex 1 with bis(catecholato)diboron (B₂Cat₂) allows for the synthesis of nickel(ii) bis-boryl complex 3 that promotes the clean and reversible heterolytic cleavage of dihydrogen leading to the formation of dihydroborate nickel complex 4. Density functional theory analysis of this reaction revealed that the heterolytic activation of H₂ is facilitated by the cooperation of both boryl moieties and the metal atom in a concerted mechanism that involves a Ni(ii)/Ni(0)/Ni(ii) process. Contrary to 1, the boron atom from the PBP ligand in 3 behaves as a nucleophile, accepting a formally protic hydrogen, whereas the catecholboryl moiety acts as an electrophile, receiving the attack from the hydride-like fragment. This manifests the dramatic change in the electronic properties of a ligand by tuning the substituent trans to it and constitutes an unprecedented cooperative mechanism that involves two boryl ligands in the same molecule operating differently, one as a Lewis acid and the other one as a Lewis base, in cooperation with the metal. In addition, reactivity towards different nucleophiles such as amines or ammonia confirmed the electrophilic nature of the Bcat moiety, allowing the formation of aminoboranes.

A bis(boryl)nickel complex promotes the facile and reversible activation of H₂ through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process.     

Reaction of 2H-azirine phosphine oxide and -phosphonates with nucleophiles. Stereoselective Synthesis of functionalized aziridines and alpha- and beta-aminophosphorus derivatives

[reaction: see text] A simple and efficient stereoselective synthesis of aziridine-2-phosphonate 3, and -phosphine oxide 5 by diastereoselective addition of Grignard reagents to 2H-azirine phosphonate 1 and -phosphine oxide 4 is reported. Similarly, the addition of heterocyclic amines and benzenethiol to aziridines 1 and 4 yielded functionalized aziridines 10, 11, and 18. These aziridines are used as intermediates for the regioselective synthesis of beta-aminophosphine oxides 6 and beta-aminophosphonates 7, as well as alpha- aminophosphonates 8. Phenylsulfenyl-substituted alpha-aminophosphorus derivatives 15 and 19 are obtained directly from benzenethiol and 2H-azirine phosphonates 1 and -phosphine oxides 4.     

Reactivity of 2-deoxy-2-iodoglycosyl isothiocyanates with O-, S-, and N-nucleophiles. Synthesis of glycopyranoso-fused thiazoles

The reactivity of 2-deoxy-2-iodoglycosyl isothiocyanates toward O- and S-nucleophiles gives an easy access to 2-deoxy-2-iodoglycopyranosyl thiocarbamates and dithiocarbamates. Internal nucleophilic displacement of the iodine by the sulfur atom in these compounds allows the preparation of glycopyranoso[1,2-d]-1,3-thiazoles and glycopyranoso[1,2-d]-1,3-thiazolidin-2-one or -2-thione. Reaction with amines or polyamines as N-nucleophiles led directly to 2-aminoglycopyranoso[1,2-d]-1,3-thiazoles without isolation of the intermediate thioureas. Methyl 2-deoxy-2-iodoglycopyranosyl thiocarbamates also allow the synthesis of 2-deoxyglycopyranosyl thiocarbamates or 2-deoxy-2-iodoglycopyranosyl carbamates.     

SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5′-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization (k₁) from Z to N in the excited state. Some of these parameters (f_N, Δv, Q_N, k₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.     

Two thiourea‐containing gold(I) complexes

The crystal structures of two salts of bis­(thio­urea)­gold(I) complexes, namely bis­(thio­urea‐κS)­gold(I) chloride, [Au(CH₄N₂S)₂]Cl, (I), and bis­[bis­(thio­urea‐κS)­gold(I)] sulfate, [Au(CH₄N₂S)₂]₂SO₄, (II), have been determined. The chloride salt, (I), is isomorphous with the corresponding bromide salt, although there are differences in the bonding. The Au^I ion is located on an inversion centre and coordinated by two symmetry‐related thio­urea ligands through the lone pairs on their S atoms [Au—S 2.278 (2) Å and Au—S—C 105.3 (2)°]. The sulfate salt, (II), crystallizes with four independent [Au(CH₄N₂S)₂]⁺ cations per asymmetric unit, all with nearly linear S—Au—S bonding. The cations in (II) have similar conformations to that found for (I). The Au—S distances range from 2.276 (3) to 2.287 (3) Å and the Au—S—C angles from 173.5 (1) to 177.7 (1)°. These data are relevant in interpreting different electrochemical processes where gold–thio­urea species are formed.