Synthesis of Multinuclear Organometallic Cage Complexes with Structurally Unique Cyclophosphate Ligand and Their Application for Inorganic Materials

点击翻译按钮获取中文摘要

We have found that a series of organometallic cage complexes can be synthesized by using cyclophosphate ions and Cp^*Ti units. The reaction of the cyclotetraphosphate ion (P_4O_<12>^<4->) with [Cp^*TiCl_3] (Cp^*=η^5-C_5Me_5) gives [(Cp^*Ti)_2(P_4O_<12>^<4->)_2]^<2-> where the P_4O_<12> ligands adopt a saddle conformation, while that with [(CpTiCl)_3(μ-O)_3] leads to [(Cp^*Ti)_3(μ-O)_3(P_4O_<12>)]^- containing a crown form P_4O_<12> ligand ; both products feature their unique cage structures. On the other hand, the reactions of the cyclotriphosphate ion (P_3O_9^<3->) with [(CpTiCl_2)_2(μ-O)] and [(CpTiCl)_3(μ-O)_3] afford [(Cp^*Ti)_2(μ-O)(P_3O_9)_3]^<2-> and [(Cp^*Ti)_3(μ-O)_3Cl(P_3O_9)]^-, respectively, and in both cases the P_3O_3 ligands bridge two titanium centers with an η^2:η^1 mode.We have also shown that reactions of [M(MeO)(diene)]_2 (M=Rh,Ir) with organophosponate RPO_3H_2 (R=Ph,^tBu) give rise to formation of a series of dinuclear complexes [{M(diene)}_4(RPO_3)_2], whose crystallographic analysis revealed three distinct types of solid state structures. These complexes are fluxional in solution and their spectral analysis indicates that the four metal fragment are equivalent in the NMR time scale.Reactivities of the cyclotriphosphato complexes of ruthenium have been investigate in detail from the viewpoint of a molecular model of the hydroxyapatite-supported ruthenium catalyst. Photolysis of (PPN)[Ru(P_3O_9)(C_6H_6)] (PPN=(Ph_3P)_2N^+) in the presence of bpy (2,2'-bipyridine) and ROH (R=Me,Et,Ph) affords the alcohol or phenol complexes (PPN)[Ru(P_3O_9)(ROH)(bpy)]. These complexes are oxidized during recrystallization to give the Ru(III) alkoxo or phenoxo complexes (PPN)[Ru(P_3O_9)(RO)(bpy)]. Treatment of the alcohol complex with cyclopentene or internal alkynes leads to the η^2-alkene or η^2-alkyne complexes, while that with terminal alkynes in alcohols affords the alkoxycarbene complexes.