Reduction of Nitrogen Oxides by Hydrogen with Rhodium(I)-Platinum(II) Olefin Complexes as Catalysts

The nitrogen oxides NO₂ , NO, and N₂ O are among the most potent air pollutants of the 21^st century. A bimetallic Rh^I -Pt^II complex containing an especially designed multidentate phosphine olefin ligand is capable of catalytically detoxifying these nitrogen oxides in the presence of hydrogen to form water and dinitrogen as benign products. The catalytic reactions were performed at room temperature and low pressures (3-4 bar for combined nitrogen oxides and hydrogen gases). A turnover number (TON) of 587 for the reduction of nitrous oxide (N₂ O) to water and N₂ was recorded, making these Rh^I -Pt^II complexes the best homogeneous catalysts for this reaction to date. Lower TONs were achieved in the conversion of nitric oxide (NO, TON=38) or nitrogen dioxide (NO₂ , TON of 8). These unprecedented homogeneously catalyzed hydrogenation reactions of NO_x were investigated by a combination of multinuclear NMR techniques and DFT calculations, which provide insight into a possible reaction mechanism. The hydrogenation of NO₂ proceeds stepwise, to first give NO and H₂ O, followed by the generation of N₂ O and H₂ O, which is then further converted to N₂ and H₂ O. The nitrogen-nitrogen bond-forming step takes place in the conversion from NO to N₂ O and involves reductive dimerization of NO at a rhodium center to give a hyponitrite (N₂ O₂ ^2- ) complex, which was detected as an intermediate.