Quantum mechanical calculations were performed on the previously reported synthetically isolated cAAC stabilized borylene complexes1 and iron complexes,2 employed for the reduction of N2 using DFT, NBO, QTAIM and EDA-NOCV methods. Calculations at M062X-D3/Def-2TZVPP level, suggest the formation of 4a from 1a via either route is exergonic. Nevertheless, the overall exergonicity value obtained from route-1 (-216.8 kcal/mol) is considerably higher than that obtained from route-2 (-24.4 kcal/mol), indicating that route-1 is more likely to carry out the reaction in the forward direction. The values of Wiberg bond index (WBI) values and ellipticity values from AIM analysis correlate well with each other and suggest a single bond character of the cAACB bond in the starting complex 1a and a cAAC=B double bond in transient species 2a and radical species 5a. The intrinsic interactions and relative orbital contributions from EDA-NOCV calculations, illustrate that the BN bond is stronger and more covalent than that of the FeN bond, which clarifies the fundamental reason for the inefficiency of the boron complexes in the effective catalytic reduction of nitrogen. However, changing the ligand from Dur (2a) to N(SiMe3)2 (2b) results in a decrease in the HOMO-LUMO energy gap, indicating that 2b has a relatively high lability and can be suggested as a better alternative to the previously reported durene substituted complex (1a) for the activation of N2.

STABILITY AND BONDING ANALYSIS OF CARBENE-BORYLENE BONDED DINITROGEN COMPLEXES - A DEEPER INSIGHT

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27th CRSI National Symposium in Chemistry

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