20621-02-7Relevant articles and documents
Nickel-mediated N-N bond formation and N2O liberationvianitrogen oxyanion reduction
Beagan, Daniel M.,Cabelof, Alyssa C.,Carta, Veronica,Caulton, Kenneth G.,Gao, Xinfeng,Pink, Maren
, p. 10664 - 10672 (2021/08/20)
The syntheses of (DIM)Ni(NO3)2and (DIM)Ni(NO2)2, where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin)2. Single deoxygenation of (DIM)Ni(NO2)2yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ1-ONO. Further deoxygenation of (DIM)Ni(NO)(ONO) results in the formation of dimeric [(DIM)Ni(NO)]2, where the dimer is linked through a Ni-Ni bond. The lost reduced nitrogen byproduct is shown to be N2O, indicating N-N bond formation in the course of the reaction. Isotopic labelling studies establish that the N-N bond of N2O is formed in a bimetallic Ni2intermediate and that the two nitrogen atoms of (DIM)Ni(NO)(ONO) become symmetry equivalent prior to N-N bond formation. The [(DIM)Ni(NO)]2dimer is susceptible to oxidation by AgX (X = NO3?, NO2?, and OTf?) as well as nitric oxide, the latter of which undergoes nitric oxide disproportionation to yield N2O and (DIM)Ni(NO)(ONO). We show that the first step in the deoxygenation of (DIM)Ni(NO)(ONO) to liberate N2O is outer sphere electron transfer, providing insight into the organic reductants employed for deoxygenation. Lastly, we show that at elevated temperatures, deoxygenation is accompanied by loss of DIM to form either pyrazine or bipyridine bridged polymers, with retention of a BpinO?bridging ligand.
Tracking reactive intermediates by FTIR monitoring of reactions in low-temperature sublimed solids: Nitric oxide disproportionation mediated by ruthenium(II) carbonyl porphyrin Ru(TPP)(CO)
Azizyan, Arsen S.,Kurtikyan, Tigran S.,Martirosyan, Garik G.,Ford, Peter C.
, p. 5201 - 5205 (2013/06/05)
Interaction of NO (15NO) with amorphous layers of Ru(II) carbonyl porphyrin (Ru(TPP)(CO), TPP2- = meso-tetraphenylporphyrinato dianion) was monitored by FTIR spectroscopy from 80 K to room temperature. An intermediate spectrally char
Surface-nitrogen removal in a steady-state NO + H2 reaction on Pd(110)
Ma, Yunsheng,Matsushima, Tatsuo
, p. 1256 - 1261 (2007/10/03)
Surface-nitrogen removal steps were analyzed in the course of a catalyzed NO + H2 reaction on Pd(110) by angle-resolved mass spectroscopy combined with cross-correlation time-of-flight techniques. Four removal steps, i.e., (i) the associative process of nitrogen atoms, 2N(a) → N 2(g), (ii) the decomposition of the intermediate, NO(a) + N(a) → N2O(a) → N2(g) + O(a), (iii) its desorption, N 2O(a) → N2O(g), and (iv) the desorption as ammonia, N(a) + 3H(a) → NH3(g), are operative in a comparable order. Above 600 K, process (i) is predominant, whereas the others largely contribute below 600 K. Process (iv) becomes significant at H2 pressures above a critical value, about half the NO pressure. Hydrogen was a stronger reagent than CO toward NO reduction and relatively enhanced the N(a) associative process.
