6629-91-0Relevant articles and documents
PHOTOELECTRONIC SPECTRUM AND ELECTRONIC STRUCTURE OF FORMALDEHYDE HYDRAZONE
Zverev, V. V.,Bazhanova, Z. G.,Vovna, V. I.
, p. 328 - 329 (1993)
During the thermal decomposition of a polymer obtained by the reaction of hydrazine with formaldehyde, the photoelectronic spectrum of formaldehyde hydrazone H2N-N-CH2 was determined.The spectrum was identified by the MNDO method and in a n-? approximation.The properties of H2N-N-CH2 in the initial state and during disturbance of the n-? interaction were compared.
Electrochemical Reductive N-Methylation with CO2Enabled by a Molecular Catalyst
Rooney, Conor L.,Wu, Yueshen,Tao, Zixu,Wang, Hailiang
supporting information, p. 19983 - 19991 (2021/12/01)
The development of benign methylation reactions utilizing CO2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, we report the first electrochemical reductive N-methylation reaction with CO2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO2, with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO2 and nitro-compounds are reduced concurrently to yield N-methylamines with high monomethylation selectivity via the overall transfer of 12 electrons and 12 protons.
Preparation, crystal structure and mechanism of formation of a novel dinuclear carbopentazane complex, >2
Heaton, Brian T.,Jacob, Chacko,Monks, Gary L.,Hursthouse, Michael B.,Ghatak, Indira,Somerville, Richard G. et al.
, p. 61 - 68 (2007/10/03)
The reaction of Rh(NO3)3*2H2O with PPh3 and N2H4*H2O in MeOH gave the dinuclear carbopentazane complex >(2+) 1, which has been characterised by multinuclear NMR measurements and X-ray diffraction.It is a dipositive, dinuclear cation in which the two bis(triphenylphosphine)rhodium units are bridged by the tetradentate carbopentazane ligand.The rhodium atoms have the expected square-planar geometry, with Rh-P and Rh-N distances of 2.225(3)-2.253(3) and 2.130(6)-2.166(6) Angstroem respectively.A series of experiments, aimed at elucidating the mechanism of formation of 1, indicated that the formation of the NCH2N linkage occurs via acid-catalysed nucleophilic addition of free N2H4 to the CH2 group of an NH2N=CH2 ligand co-ordinated to Rh1, and unambiguous multinuclear NMR (13C, 15N and 31P) and mass spectrometric evidence has been obtained for the monomeric complex (1+), which readily rearranges to form 1.Related experiments have also provided evidence for the formation of (1+), which also rearranges to give a dinuclear complex, >(2+).
