Unravelling the potential of low-valent tunable vanadium complexes in the nitrogen reduction reaction (NRR).

Density functional theory calculations have been carried out to investigate the potential of several hitherto unknown low-valent tripodal vanadium complexes towards conversion of dinitrogen to ammonia as a function of different equatorial (PPr and SPr) and bridgehead groups (B, C and Si). All the newly proposed vanadium complexes were probed towards understanding their efficiency in some of the key steps involved in the dinitrogen fixation process. They were found to be successful in preventing the release of hydrazine during the nitrogen reduction reaction.

Mono(Lewis Base)-Stabilized Gallium Iodide: An Unexplored Class of Promising Ligands.

Quantum-chemical (DFT) calculations on hitherto unknown base(carbene)-stabilized gallium monoiodides (LB→GaI) suggest that these systems feature one lone pair of electrons and a formally vacant p-orbital - both centered at the central gallium atom - and exhibit metallomimetic behavior. The calculated reaction free energies as well as bond dissociation energies suggest that these LB→GaI systems are capable of forming stable donor-acceptor complexes with group 13 trichlorides. Examination of the ligand exchange reactions with iron and nickel complexes indicates their potential use as ligands in transition metal chemistry.

Skeletally substituted aluminium and gallium carbenoids: a computational exploration.

Comprehensive computational investigations were carried out to understand the electronic and ligand properties of skeletally substituted β-diketiminate stabilized Al(I) and Ga(I) carbenoids as well as to probe their potential in small molecule activation. All of the proposed group 13 carbenoids possess a stable singlet ground state, and the majority of them have a significantly enhanced electron donation ability compared to the experimentally reported systems. The evaluation of the energetics associated with the splitting of various strong bonds such as H-H, N-H, C-F, and B-H by these carbenoids indicates that many of the proposed Al and Ga carbenoids may be considered as suitable candidates for small molecule activation.