Reaction Properties of the <i>trans</i>-Hyponitrite Complex [Ru<sub>2</sub>(CO)<sub>4</sub>(μ-H)(μ-PBu<i><sup>t</sup></i><sup></sup><sub>2</sub>)(μ-Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2</sub>)(μ-η<sup>2</sup>-ONNO)]
收藏资源简介：
The protonation of [Ru2(CO)4(μ-H)(μ-PBut2)(μ-dppm)(μ-η2-ONNO)] (1) with HBF4 occurs at the oxygen of the noncoordinating side of the trans-hyponitrite ligand to give [Ru2(CO)4(μ-H)(μ-PBut2)(μ-dppm)(μ-η2-ONNOH)][BF4] (2) in good yield. The monoprotonated hyponitrite in 2 is deprotonated easily by strong bases to regenerate 1. Furthermore, 1 reacts with the methylating reagent [Me3O][BF4] to afford [Ru2(CO)4(μ-H)(μ-PBut2)(μ-dppm)(μ-η2-ONNOMe)][BF4] (3). The molecular structures of 2 and 3 have been determined crystallographically, and the structure of 2 is discussed with the results of the DFT/B3LYP calculations on the model complex [Ru2(CO)4(μ-H)(μ-PH2)(μ-H2PCH2PH2)(μ-η2-ONNOH)]+ (2a). Moreover, the thermolysis of 2 in ethanol affords [Ru2(CO)4(μ-H)(μ-OH)(μ-PBut2)(μ-dppm)][BF4] (4) in high yield, and the deprotonation of 4 by DBU in THF yields the novel complex [Ru2(CO)4(μ-OH)(μ-PBut2)(μ-dppm)] (5).
