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

我们发现用环磷酸根离子和Cp^*Ti单元可以合成一系列有机金属笼状配合物。环四磷酸离子（P_4O_<12>^<4->）与[Cp^*TiCl_3] （Cp^*=η^5-C_5Me_5）反应得到[(Cp^*Ti)_2(P_4O_<12>^<4->)_2]^<2->，其中P_4O_<12>配体呈鞍状构象，而与[(CpTiCl)_3(μ-O)_3]反应得到[(Cp^*Ti)_3(μ-O)_3(P_4O_<12>)]^-含冠状P_4O_<12>配体；这两种产品都有其独特的笼型结构。另一方面，环三磷酸离子（P_3O_9^<3->）与[(CpTiCl_2)_2(μ-O)]和[(CpTiCl)_3(μ-O)_3]的反应分别产生[(Cp^*Ti)_2(μ-O)(P_3O_9)_3]^<2->和[(Cp^*Ti)_3(μ-O)_3Cl(P_3O_9)]^-，在这两种情况下，P_3O_3配体以η^2:η^1模式桥接两个钛中心。[M(MeO)（二烯）]_2 （M=Rh,Ir）与有机膦酸盐RPO_3H_2 （R=Ph,^tBu）反应可生成一系列双核配合物[{M（二烯）}_4(RPO_3)_2]，其晶体学分析显示出三种不同类型的固态结构。这些配合物在溶液中是有通量的，它们的光谱分析表明四个金属碎片在核磁共振时间尺度上是等效的。从羟基磷灰石负载钌催化剂的分子模型出发，对钌环三磷酸配合物的反应性进行了详细的研究。（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生成Ru（III）烷氧或苯氧配合物（PPN）[Ru(P_3O_9)(RO)(bpy)]。醇配合物与环戊烯或内炔处理得到η^2-烯烃或η^2-炔配合物，而与醇中的末端炔处理得到烷氧羰基配合物。

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.