Observation and mechanism of cryo N₂ cleavage by a tantalum cluster

Abstract

Twofold cryo N2 cleavage by Ta4+ clusters occurs via a multistep across edge-above surface (AEAS) mechanism across submerged barriers.

Dinitrogen Activation by Heteronuclear Metal Carbide Cluster Anions FeTaC2–: A 5d Early and 3d Late Transition Metal Strategy

“…Gas-phase studies with readily produced and properly characterized atomic clusters provide an ideal way to study the chemical reactions and reveal relevant atomistic mechanisms that would hardly be attainable for classical condensed-phase studies. − Considering the important role of iron and carbon in industrial and biological nitrogen fixation and the outstanding performance of tantalum clusters in the activation of N 2 , , herein gas-phase cluster anions comprising Fe (3d-LTM), Ta (5d-ETM), and C elements were prepared, and their reactions with N 2 were studied at room temperature. Remarkably, the FeTaC 2 – anion with only one ETM atom was identified for the first time to enable the thermal cleavage of NN bond by a polarized Fe–Ta bond.…”

Reaction of Ta3– Clusters with Molecular Nitrogen: A Mechanism Investigation

“…However, in the Ta 4 + /N 2 system studied by Fries et al, this step requires merely an activation of 5 kJ mol –1 . 45 …”

Mutual functionalization of dinitrogen and methane mediated by heteronuclear metal cluster anions CoTaC2−

“…Isolated gas-phase atomic clusters are important model systems for the precise design of desired active sites and the fundamental understanding of bond activation and formation processes. 11 The activation and individual functionalization of N 2 or CH 4 , [12][13][14][15][16][17][18] and the formation of N-C bonds [19][20][21][22][23][24][25] are also extensively studied issues in the gas-phase eld. Typical examples of N-C bond formation from N 2 or CH 4 in gas-phase studies can be classied as follows: (i) reactions of metal carbide clusters with N 2 [22][23][24][25] or metal nitride clusters with CH 4 , 26,27 and (ii) coupling reactions of CH 4 with NH 3 28,29 or N 2 with CO 2 .…”