Aminonitrile rearrangement and the cleavage of 1,1-dialkyl-δ2-tetrahydropyridazinium salts

1,1-Dimethyl- and 1-ethyl-1-methyl-²-tetrahydropyridazinium iodides undergo an aminonitrile rearrangement under the action of alkali with the formation of-dialkylaminobutyronitriles.The aminonitrile rearrangement has been used as a method of showing the structure of the oxidation product of 3-methylhexahydropyridazine which is 6-methyl-²-tetrahydropyridazine.Under the action ot NaOH, 3-methyl-substituted ²-tetrahydropyridazinium salts, for which the aminonitrile rearrangement is excluded split off the substituent from the nitrogen atom and undergo far-reaching decomposition.     

Temperature- and substituent-dependence in the photosensitized oxygenation of N,N-disubstituted hydrazones

Methylene blue-sensitized photooxidation of N,N-disubstituted hydrazones $\text{1a-f}$ gave various products $\text{2-9}$, depending on the reaction temperature and N-substituents. The major reaction modes from the photo-oxidation of N,N-diphenylhydrazones were α-oxidation at room temperature and C=N cleavage at ?78 °C in contrast to C=N cleavage as an only reaction mode for the photooxidation of N,N-dimethylhydrazones at either room temperature or ?78 °C.     

Homogeneous molecular catalysis of the electrochemical reduction of N2O to N2: redox vs. chemical catalysis

Homogeneous electrochemical catalysis of N₂O reduction to N₂ is investigated with a series of organic catalysts and rhenium and manganese bipyridyl carbonyl complexes. An activation-driving force correlation is revealed with the organic species characteristic of a redox catalysis involving an outer-sphere electron transfer from the radical anions or dianions of the reduced catalyst to N₂O. Taking into account the previously estimated reorganization energy required to form the N₂O radical anions leads to an estimation of the N₂O/N₂O˙⁻ standard potential in acetonitrile electrolyte. The direct reduction of N₂O at a glassy carbon electrode follows the same quadratic activation driving force relationship. Our analysis reveals that the catalytic effect of the mediators is due to a smaller reorganization energy of the homogeneous electron transfer than that of the heterogeneous one. The physical effect of “spreading” electrons in the electrolyte is shown to be unfavorable for the homogeneous reduction. Importantly, we show that the reduction of N₂O by low valent rhenium and manganese bipyridyl carbonyl complexes is of a chemical nature, with an initial one-electron reduction process associated with a chemical reaction more efficient than the simple outer-sphere electron transfer process. This points to an inner-sphere mechanism possibly involving partial charge transfer from the low valent metal to the binding N₂O and emphasizes the differences between chemical and redox catalytic processes.

Homogeneous electrochemical catalysis of N₂O reduction to N₂ is investigated with a series of organic catalysts and rhenium and manganese bipyridyl carbonyl complexes.     

Synthesis, structure, and electrochemical properties of a family of 2-(arylazo)phenolate complexes of ruthenium with unusual C-C coupling and N=N cleavage

Reaction of 2-(4'-R-phenylazo)-4-methylphenols (R = OCH3, CH3, H, Cl, and NO2) with [Ru(dmso)(4)Cl2]affords a family of five ruthenium(III) complexes, containing a 2-(arylazo)phenolate ligand forming a six-membered chelate ring and a tetradentate ligand formed from two 2-(arylazo)phenols via an unusual C-C coupling linking the two ortho carbons of the phenyl rings in the arylazo fragment. A similar reaction with 2-(2'-methylphenylazo)-4-methylphenol with [Ru(dmso)(4)Cl2] has afforded a similar complex, in which one 2-(2'-methylphenylazo)-4-methylphenolate ligand is coordinated forming a six-membered chelate ring, and the other two ligands have undergone the C-C coupling reaction, and the coupled species is coordinated as a tetradentate ligand forming a five-membered N,O-chelate ring, a nine-membered N,N-chelate ring, and another five-membered chelate ring. Reaction of 2-(2',6'-dimethylphenylazo)-4-methylphenol with [Ru(dmso)(4)Cl2] has afforded a complex in which two 2-(2',6'-dimethylphenylazo)-4-methylphenols are coordinated as bidentate N,O-donors forming five- and six-membered chelate rings, while the third one has undergone cleavage across the N=N bond, and the phenolate fragment, thus generated, remains coordinated to the metal center in the iminosemiquinonate form. Structures of four selected complexes have been determined by X-ray crystallography. The first six complexes are one-electron paramagnetic and show rhombic ESR spectra. The last complex is diamagnetic and shows characteristic 1H NMR signals. All the complexes show intense charge-transfer transitions in the visible region and a Ru(III)-Ru(IV) oxidation on the positive side of SCE and a Ru(III)-Ru(II) reduction on the negative side.     

ENDOR/HYSCORE studies of the common intermediate trapped during nitrogenase reduction of N2H2, CH3N2H, and N2H4 support an alternating reaction pathway for N2 reduction

Enzymatic N(2) reduction proceeds along a reaction pathway composed of a sequence of intermediate states generated as a dinitrogen bound to the active-site iron-molybdenum cofactor (FeMo-co) of the nitrogenase MoFe protein undergoes six steps of hydrogenation (e(-)/H(+) delivery). There are two competing proposals for the reaction pathway, and they invoke different intermediates. In the 'Distal' (D) pathway, a single N of N(2) is hydrogenated in three steps until the first NH(3) is liberated, and then the remaining nitrido-N is hydrogenated three more times to yield the second NH(3). In the 'Alternating' (A) pathway, the two N's instead are hydrogenated alternately, with a hydrazine-bound intermediate formed after four steps of hydrogenation and the first NH(3) liberated only during the fifth step. A recent combination of X/Q-band EPR and (15)N, (1,2)H ENDOR measurements suggested that states trapped during turnover of the α-70(Ala)/α-195(Gln) MoFe protein with diazene or hydrazine as substrate correspond to a common intermediate (here denoted I) in which FeMo-co binds a substrate-derived [N(x)H(y)] moiety, and measurements reported here show that turnover with methyldiazene generates the same intermediate. In the present report we describe X/Q-band EPR and (14/15)N, (1,2)H ENDOR/HYSCORE/ESEEM measurements that characterize the N-atom(s) and proton(s) associated with this moiety. The experiments establish that turnover with N(2)H(2), CH(3)N(2)H, and N(2)H(4) in fact generates a common intermediate, I, and show that the N-N bond of substrate has been cleaved in I. Analysis of this finding leads us to conclude that nitrogenase reduces N(2)H(2), CH(3)N(2)H, and N(2)H(4) via a common A reaction pathway, and that the same is true for N(2) itself, with Fe ion(s) providing the site of reaction.     

Selective cleavage of polycyclic cyclopropanes by electrochemical oxidation

Anodic oxidation in acetic acid of polycyclic cyclopropanes, namely tricyclene, cyclofenchene, and longicyclene, followed by hydrolysis brought about stereo- and regioselective formation of the corresponding homoallylic alcohols as the main product in good yields.     

The electrochemical reaction of nitrate in N,N-dimethylformamide

Polarography, cyclic voltammetry and controlled-potential coulometry were used to study N,N-dimethylformamide solutions of nitrate. Nitrate is reversibly reduced in a one-electron step to NO(2). The diffusion coefficient of nitrate was polarographically estimated to be 4.6 x 10(-6) cm(2)/sec. Polarography in dimethylformamide was found to be a convenient method of analysis for nitrate in a solid fertilizer.     

Studies of the electrochemical reduction of some dinitroaromatics

The electrochemical reduction of a series of dinitroaromatics, along with one trinitro compound, has been investigated at a glassy carbon electrode in N,N-dimethylformamide. The separation between the two standard potentials for the reduction, E°₁ − E°₂, has been determined and discussed in terms of the structures of the compounds. cis-4,4′-Dinitrostilbene was shown to undergo redox-catalyzed isomerization to the trans isomer. This was demonstrated with partial controlled potential electrolysis followed by chromatographic analysis of the solution. It was also found that redox-catalyzed isomerization could adequately account for the voltammetric behavior. The anion radicals of 3,5-dinitropyridine and 1,3,5-trinitrobenzene undergo reversible dimerization reactions. The rate and equilibrium constants for the dimerization were determined by simulation of the voltammograms of these two compounds and also by simulation of the voltammograms obtained with solutions from the one-electron controlled potential reduction, that is, solutions of the dimer. The equilibrium constants for dimerization were also determined by electron paramagnetic resonance spectroscopy.     

Intermediates trapped during nitrogenase reduction of N triple bond N, CH3-N=NH, and H2N-NH2

A high population intermediate has been trapped on the nitrogenase active site FeMo cofactor during reduction of N2. In addition, intermediates have been trapped during reduction of CH3-N=NH by the alpha-195Gln variant and during reduction of H2N-NH2 by the alpha-70Ala/alpha-195Gln variant. Each of these trapped states shows an EPR signal arising from an S = 1/2 state of the FeMo cofactor. 15N ENDOR shows that each intermediate has a nitrogenous species bound to the FeMo cofactor, with a single type of N seen for each bound intermediate. The g tensors are unique to each intermediate, g(e) = [2.084, 1.993, 1.969], g(m) = [2.083, 2.021, 1.993], g(l) = [2.082, 2.015, 1.987], as are the 15N hyperfine couplings at g1, which suggests that three distinct stages of NN reduction may have been trapped. The 1H ENDOR spectra show that the N2 intermediate is at a distinct and earlier stage of reduction from the other two, so at least two stages of NN reduction have been trapped. Some possible structures of the hydrazine intermediate are presented.     

Radical intermediates in the electrochemical reduction of alizarin

Conclusions In the electroreduction of alizarin in an aprotic medium the stepwise formation of the anion-radical and subsequently of the dianion has been observed; under conditions of the prolonged process the anion-radical disproportionates and through intermediate stages of deprotonation and reduction is converted into the stable dianion-radical.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 983–988, May, 1985.     

Mediated electrochemical reduction of 1,1-dichlorocyclopropanes

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 261–262, January, 1991.