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

我们发现用环磷酸盐离子和Cp^*Ti单元可以合成一系列有机金属笼状络合物。环四磷酸根与[Cp^*TiCl3](Cp^*=[(Cp^*Ti)_2(P_4O_&lt；12&gt；^&lt；4-&gt；)_2]^&lt；2-&gt；^5-C_5Me_5)反应生成η，其中P_4O_12&gt；[(CpTiCl)_3(μ-O)_3]与[(CpTiCl)_3(μ-O)_3]形成[(Cp^*Ti)_3(Cp-O)_3(P_4O_&lt；12&gt；)]^-冠状P_4O_1；另一方面，环三磷酸根离子与[(CpTiCl2)2(μ-O)]和[(CpTiCl3(μ-O)3]反应生成[(CpTiCl2)2(μ-O)(P3O9)3]^&lt；2-gt；和[(Cp^*Ti)_3(μ-O)_3Cl(P_3O_9)]^-，P_3O_3配体以η^2：η^1方式连接两个钛中心。这些配合物在溶液中是流动的，它们的光谱分析表明这四个金属碎片在核磁共振时间尺度上是等价的。从羟基磷灰石负载的Ru催化剂的分子模型的观点出发，详细研究了这些环三磷配合物的反应活性。(PPN)[Ru(P_3O_9)(C_6H_6)](PPN=(Ph_3P)_2N^+)在BPY(2，2‘-联吡啶)和ROH(R=Me，Et，Ph)存在下光解得到醇或苯酚配合物(PPN)[Ru(P_3O_9)(ROH)(Bpy)]。这些配合物在重结晶过程中被氧化，得到Ru(III)烷氧基或酚氧基配合物(PPN)[Ru(P_3O_9)(RO)(Bpy)]。醇类化合物与环戊烯或内炔反应生成η^2-烯烃或η^2-炔烃络合物，而与醇中末端炔烃反应生成烷氧卡宾络合物。

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.