Nickel(II) Complexes of Tripodal Ligands as Catalysts for Fixation of Atmospheric CO2 as Organic Carbonates

Abstract

The fixation of atmospheric CO₂ into value-added products is a promising methodology. A series of novel nickel(II) complexes of the type [Ni(L)(CH₃ CN)₂ ](BPh₄ )₂ 1-5, where L=N,N-bis(2-pyridylmethyl)-N', N'-dimethylpropane-1,3-diamine (L1), N,N-dimethyl-N'-(2-(pyridin-2-yl)ethyl)-N'-(pyridin-2-ylmethyl) propane-1,3-diamine (L2), N,N-bis((4-methoxy-3,5-dimethylpyridin-2-ylmethyl)-N',N'-dimethylpropane-1,3-diamine (L3), N-(2-(dimethylamino) benzyl)-N',N'-dimethyl-N-(pyridin-2-ylmethyl) propane-1,3-diamine (L4) and N,N-bis(2-(dimethylamino)benzyl)-N', N'-dimethylpropane-1,3-diamine (L5) have been synthesized and characterized as the catalysts for the conversion of atmospheric CO₂ into organic cyclic carbonates. The single-crystal X-ray structure of 2 was determined and exhibited distorted octahedral coordination geometry with cis-α configuration. The complexes have been used as a catalyst for converting CO₂ and epoxides into five-membered cyclic carbonates under 1 atmospheric (atm) pressure at room temperature in the presence of Bu₄ NBr. The catalyst containing electron-releasing -Me and -OMe groups afforded the maximum yield of cyclic carbonates, 34% (TON, 680) under 1 atm air. It was drastically enhanced to 89% (TON, 1780) under pure CO₂ gas at 1 atm. It is the highest catalytic efficiency known for CO₂ fixation using nickel-based catalysts at room temperature and 1 atm pressure. The electronic and steric factors of the ligands strongly influence the catalytic efficiency. Furthermore, all the catalysts can convert a wide range of epoxides (ten examples) into corresponding cyclic carbonate with excellent selectivity (>99%) under this mild condition.

Keywords: Carbon dioxide fixation; Cyclic carbonates; Homogeneous Catalysis; Nickel(II) Complexes; Tripodal Ligands.