Synthesis and Substitution Reactions of Ruthenium Methanol Complexes with a Cyclophosphimato Ligand

摘要

The Ru-exchanged hydroxyapatite has recently been described to act as an effective heterogeneous catalyst for the oxidation of various organic substrates by O_2. In the course of our study on organometallic derivatives of cyclophospahtes, these reports prompted us to investigate the reactivities of cyclophosphato complexes of ruthenium, the backbone of which resembles the surface structure of hydroxyapatite. Previously we have reported that the photolysis of (PPN)[Ru(P_3O_9)(C_6H_6)] (PPN = (Ph_3P)_2N~+) in ROH in the presence of a bidentate ligand (L) affords the Ru(II) alcohol complex (PPN)[Ru(P_3O_9)(L)-(ROH)] (1; L = bpy (2,2'-bipyridyl), dppe (Ph_2PCH_2CH_2PPh_2)), which undergoes further ligand substitution with small molecules such as alkenes, alkynes, or N_2 to produce eta~2-alkene, eta~2-alkyne, alkoxycarbene, vinylidene, carbonyl, or dinitrogen complexes. In contrast, little has been known for the reactivity of (PPN)[Ru{P_3(NH)_3O_6}(C_6H_6)] (2), which is a rare example of organometallic derivatives of cyclophosphimates [P_n(NH)_nO_(2n)]~(n-) , the amide analogs of cyclophosphates. In this study, we have examined synthesis and substitution reactions of the Ru(II) cyclotriphosphimato methanol complexes.