Plasma-promoted reactions of the heterobimetallic anions CuNb- with dinitrogen and subsequent reactions with carbon dioxide: formation of C-N bonds.

The activation and functionalization of dinitrogen with carbon dioxide into useful chemicals containing C-N bonds are significant research projects but highly challenging. Herein, we report that N2 molecules are dissociated by heterobimetallic CuNb- anions assisted by surface plasma radiation, leading to the formation of CuNbN2- anions; the CuNbN2- anions can further react with CO2 to generate products NCO- with one C-N bond and NbO2NCN- with two C-N bonds under thermal collision conditions. For the activation of dinitrogen, the plasma atmosphere is conducive to the dissociation of the NN bond, which renders the coupling reactions of N2 and CO2 molecules easier to proceed. This is the first report of coupling of N2 and CO2 to generate C-N bonds by making good use of the plasma effect to assist in the activation of N2 molecules. This new strategy with the assistance of plasma provides a practicable route to construct C-N bonds by directly using N2 and CO2 at room temperature.

Conversion of carbon dioxide to a novel molecule NCNBO- mediated by NbBN2- anions at room temperature.

The activation of carbon dioxide (CO2) mediated by NbBN2- cluster anions under the conditions of thermal collision has been investigated by time-of-flight mass spectrometry combined with density functional theory calculations. Two CO double bonds in the CO2 molecule are completely broken and two C-N bonds are further generated to form the novel molecule NCNBO-. To the best of our knowledge, this new molecule is synthesized and reported for the first time. In addition, one oxygen atom transfer channel produces another product, NbBN2O-. Both of the Nb and B atoms in NbBN2- donate electrons to reduce CO2, and the carbon atom originating from CO2 serves as an electron reservoir. The reaction of NbB- with N2 was also investigated theoretically, and the formation of NbBN2- from this reaction is thermodynamically and kinetically quite favorable, indicating that NCNBO- might be produced from the coupling of N2 and CO2 mediated by NbB- anions.

Direct Conversion of N2 and O2 to Nitric Oxide at Room Temperature Initiated by Double Aromaticity in the Y2BO+ Cation.

The conversion of dinitrogen to more useful and reactive molecules has been the focus of intense research by chemists. In contrast to reductive N2 fixation, direct oxidation of N2 by O2 to nitric oxide under mild conditions via a thermochemical process is extremely challenging. Herein, we report the first example of N2 and O2 activation and coupling under thermochemical conditions through the remarkable ability of Y2BO+ to react with one N2 and two O2 molecules. Detailed mechanistic studies using mass spectrometry and quantum chemical calculations revealed that the N2 activation by Y2BO+ is facilitated by the double aromatic character of the Y2BON2+ intermediate. Subsequent oxidation with O2 releases NO in a dearomatization process driven by the formation of stronger Y-O bonds over the Y-N bonds. Our findings represent the first example of N2 and O2 activation and coupling under thermochemical conditions at room temperature, providing a novel strategy for small-molecule activation.

Dinitrogen and Carbon Dioxide Activation to Form C-N Bonds at Room Temperature: A New Mechanism Revealed by Experimental and Theoretical Studies.

In light of the current energy requirements, the conversion of CO2 and N2 into useful C-N bond-containing products under mild conditions has become an area of intense research. However, the inert nature of N2 and CO2 renders their coupling extremely challenging. Herein, nitrogen and carbon atoms originating from N2 and CO2, respectively, are fixed sequentially by NbH2- anions in the gas phase at room temperature. Isocyanate and NbO2CN- anions were formed under thermal collision conditions, thus achieving the formation of new C-N bonds directly from simple N2 and CO2. The anion structures and reaction details were studied by mass spectrometry, photoelectron spectroscopy, and quantum chemical calculations. A novel N2 activation mode (metal-ligand activation, MLA) and a related mechanism for constructing C-N bonds mediated by a single non-noble metal atom are proposed. In this MLA mode, the C atom originating from CO2 serves as an electron reservoir to accept and donate electrons.

Nitrogen Activation and Transformation on Monometallic Niobium Boron Oxide Cluster Anions at Room Temperature: A Dual-Site Mechanism.

Dinitrogen activation and transformation at room temperature is a goal that has been long sought after. Despite that, it remains underdeveloped due to being a challenging research area and the need for a better mechanistic understanding. Herein, we report that well-defined NbB3O2- gas-phase clusters can activate one N2 molecule and generate the products B3N2O- and B3N2O2-, as applying mass spectrometry and theoretical calculations. This unusual N2 activation reaction results from the different functions of the Nb and B3O2 moieties in NbB3O2-. Theoretical calculations suggest that a catalytic cycle can be completed by the recovery of NbB3O2-, which is achieved through the reactions of Nb and NbO with B3O2- and B3O-, respectively. This is the first example of N2 efficient transformation at a monometallic cluster, and this method for generating dual active sites by designing proper ligands may open the way toward the development of more effective N2 fixation and functionalization methodologies.