New Ruthenium Nitrosyl Pincer Complexes Bearing an O2 Ligand. Mono-Oxygen Transfer

We report on Ru(II)(μ2-O2) nitrosyl pincer complexes that can return to their original Ru(0) state by reaction with mono-oxygen scavengers. Potential intermediates were calculated by density functional theory (DFT) and a mechanism is proposed, revealing a new type of metal–ligand cooperation consisting of activation of the O2 moiety by both the metal center and the NO ligand. Reaction of the Ru(0) nitrosyl complex 1 with O2 quantitatively yielded the crystallographically characterized Ru(II) (μ2-O2) nitrosyl complex 2. Reaction of 2 with the mono-oxygen scavengers phosphines or CO gave the Ru(0) complex 1 and phosphine oxides, or the carbonyl complex 3 (1 trapped by CO) and CO2, respectively. Reaction of 2 with 1 equiv of phosphine at room temperature or −40 °C resulted in immediate formation of half an equivalent of 1 and 1 equiv of phosphine oxide, while half an equivalent of 2 remained unchanged. Overnight reaction at room temperature of 2 with excess CO (≥3 equiv) resulted in 3 and CO2 gas as the only...