Fixation of atmospheric CO₂ as C1-feedstock by nickel(ii) complexes

The development of molecular catalysts for the activation and conversion of atmospheric carbon dioxide (CO₂) into a value-added product is a great challenge. A series of nickel(ii) complexes, [Ni(L)(CH₃CN)₃](BPh₄)₂, 1-4 of diazepane based ligands, 4-methyl-1-[(pyridin-2-yl-methyl)]-1,4-diazepane (L1), 4-methyl-1-[2-(pyridine-2-yl)ethyl]-1,4-diazepane (L2), 4-methyl-1-[(quinoline-2-yl)-methyl]-1,4-diazepane (L3) and 1-[(4-methoxy-3,5-dimethyl-pyridin-2-yl)methyl]-4-methyl-1,4-diazepane (L4), have been synthesized and characterized as catalysts for the activation of atmospheric CO₂. The single-crystal X-ray structure of 1 shows a distorted octahedral geometry with a cis-β configuration around the NiN₆ coordination sphere. All the complexes are used as catalysts for the conversion of atmospheric CO₂ and epoxides into cyclic carbonates at 1 atmosphere (atm) pressure and in the presence of Et₃N. Catalyst 4 was found to be the most efficient catalyst and showed a 31% formation of cyclic carbonates with a TON of 620 under 1 atm air as the CO₂ source. This yield was enhanced to 94% with a TON of 1880 under 1 atm pure CO₂ gas and it is the highest catalytic efficiency known for nickel(ii)-based catalysts. Catalyst 4 enabled the transformation of a wide range of epoxides (eight examples) into corresponding cyclic carbonates with excellent selectivity (>99%) and yields of 59-94% and 11-31% under pure CO₂ and atmospheric CO₂, respectively. The catalytic efficiency is strongly influenced by the electronic nature of the complexes. The CO₂ fixation reactions without an epoxide substrate led to the formation of the carbonate bridged dinuclear nickel(ii) complexes [(LNi^II)₂CO₃](BPh₄)₂1a-4a, which are speculated as catalytically active intermediates. The formation of these species was accompanied by the formation of new absorption bands around 592-681 nm and was further confirmed by the ESI-MS and IR spectral studies. The molecular structures of these carbonate-bridged key intermediates were determined by X-ray analysis. The structures contain two Ni²⁺-centers bridged via a carbonate ion that originated from CO₂. Distorted square pyramidal geometries are adopted around each Ni(ii) center. All these results support that CO₂ fixation reactions occur via CO₂-bound nickel key intermediates.