118573-45-8Relevant academic research and scientific papers
Electrochemical reduction of bronsted acids by glassy carbon in acetonitrile-implications for electrocatalytic hydrogen evolution
McCarthy, Brian D.,Martin, Daniel J.,Rountree, Eric S.,Ullman, Alexander C.,Dempsey, Jillian L.
, p. 8350 - 8361 (2014)
Molecular catalysts for electrochemically driven hydrogen evolution are often studied in acetonitrile with glassy carbon working electrodes and Bronsted acids. Surprisingly, little information is available regarding the potentials at which acids are directly reduced on glassy carbon. This work examines acid electroreduction in acetonitrile on glassy carbon electrodes by cyclic voltammetry. Reduction potentials, spanning a range exceeding 2 V, were found for 20 acids. The addition of 100 mM water was not found to shift the reduction potential of any acid studied, although current enhancement was observed for some acids. The data reported provides a guide for selecting acids to use in electrocatalysis experiments such that direct electrode reduction is avoided.
Reversible Hydride Transfer to N,N′-Diarylimidazolinium Cations from Hydrogen Catalyzed by Transition Metal Complexes Mimicking the Reaction of [Fe]-Hydrogenase
Hatazawa, Masahiro,Yoshie, Naoko,Seino, Hidetake
, p. 8087 - 8099 (2017/07/22)
[Fe]-hydrogenase is a key enzyme involved in methanogenesis and facilitates reversible hydride transfer from H2 to N5,N10-methenyltetrahydromethanopterin (CH-H4MPT+). In this study, a reaction system was developed to model the enzymatic function of [Fe]-hydrogenase by using N,N′-diphenylimidazolinium cation (1+) as a structurally related alternative to CH-H4MPT+. In connection with the enzymatic mechanism via heterolytic cleavage of H2 at the single metal active site, several transition metal complex catalysts capable of such activation were utilized in the model system. Reduction of 1[BF4] to N,N′-diphenylimidazolidine (2) was achieved under 1 atm H2 at ambient temperature in the presence of an equimolar amount of NEt3 as a proton acceptor. The proposed catalytic pathways involved the generation of active hydride complexes and subsequent intermolecular hydride transfer to 1+. The reverse reaction was accomplished by treatment of 2 with HNMe2Ph+ as the proton source, where [(ν5-C5Me5)Ir{(p-MeC6H4SO2)NCHPhCHPhNH}] was found to catalyze the formation of 1+ and H2 with high efficiency. These results are consistent with the fact that use of 2,6-lutidine in the forward reaction or 2,6-lutidinium in the reverse reaction resulted in incomplete conversion. By combining these reactions using the above Ir amido catalyst, the reversible hydride transfer interconverting 1+/H2 and 2/H+ was performed successfully. This system demonstrated the hydride-accepting and hydride-donating modes of biologically relevant N-heterocycles coupled with proton concentration. The influence of substituents on the forward and reverse reactivities was examined for the derivatives of 1+ and 2 bearing one para-substituted N-phenyl group.
The chemistry of 1,3,5-triazacyclohexane complexes 5: Cationic zinc(II) alkyl complexes of N-alkylated 1,3,5-triazacyclohexanes and 13-benzyl-l,5,9-triazatricyclo[7.3.1.05,13]-tridecane
Haufe, Matthias,Koehn, Randolf D.,Weimann, Roman,Seifert, Guido,Zeigan, Dieter
, p. 121 - 129 (2007/10/03)
Diethylzinc reacts with hydroperchlorates of N-alkylated 1,3,5-triazacyclohexanes (R3TAC; R = methyl (Me), benzyl (Bz), isopropyl (iPr)) and with the hydrotetrafluoroborate of 1,3,5-tris-(para-fluorobenzyl)-1,3,5-triazacyclohexane (FBz3TAC) to give the corresponding cationic zinc ethyl complexes [(R3TAC)Zn(Et)][X] (X = ClO-4, BF-4). Similar complexes were obtained from diethylzinc treated with [HNMe2Ph][BF4] or [HNMe2Ph][B(C6F5)4](Et2O) in the presence of R3TAC (R = Bz, FBz, s-1-phenylethyl (s-PhMeCH)). A product of decomposition of [(Bz3TAC)Zn(Et)][ClO4] was analyzed by X-ray diffraction. The structures of [({s-PhMeCH}3TAC)Zn(Et)][BF4] and [(FBz3TAC)Zn(Et)][BF4] were estimated using nuclear Overhauser enhancement spectroscopy. Protonolysis of diethylzinc with [HNMe2Ph][BF4] in the presence of 13-benzyl-l,5,9-triazatricyclo[7.3.1.05,13]-tridecane (BzTATC) yielded the complex [(BzTATC)Zn(Et)][BF4].
PHENYL-α,α,ω-TRIHYDROPOLYFLUOROALKYLIODONIUM FLUOROBORATES
Mironova, A. A.,Soloshonok, I. V.,Maletina, I. I.,Orda, V. V.,Yagupol'skii, L. M.
, p. 530 - 535 (2007/10/02)
The reaction of difluoroiodo-α,α,ω-trihydropolyfluoroalkanes (I) with boron trifluoride and benzene gave phenyl-α,α,ω-trihydropolyfluoroalkyliodonium fluoroborates (II).It was established that the polyfluoroalkyl radical adds at the sulfur atom in reaction with p-chlorothiophenol, the N-polyfluoroalkylation product is formed with aniline, pyridine is polyfluoroalkylated at the nitrogen atom with the formnation of a quaternary salt, and a mixture of products from polyfluoroalkylation at the nitrogen atom of the dimethylamino group and at the para position of the benzene ring is formed with dimethylaniline.
