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Reaction Properties of the trans-Hyponitrite Complex [Ru2(CO)4(μ-H)(μ-PBut2)(μ-Ph2PCH2PPh2)(μ-η2-ONNO)]

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posted on 2004-10-04, 00:00 authored by Hans-Christian Böttcher, Christoph Wagner, Karl Kirchner
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).

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