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

具有独特环磷酸配体的多核有机金属笼配合物的合成及其在无机材料中的应用

• 批准号: 16550101
• 负责人: ISHII Youichi
• 金额: $ 2.37万
• 依托单位: Chuo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550101/
• 关键词: cyclotriphosphato; cyclotetraphosphato; cyclotriphosphimato; phosphonato; multinuclear complexes; titanium; ruthenium; iridium; シクロホスフェート; かご状錯体; 無機材料; シングルソースプレカーサ; シクロホスフィメート; ビニリデン; ロジウム; 三核錯体; 四核錯体

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.

我们发现，可以使用环磷酸离子和CP^*Ti单元合成一系列有机笼复合物。环磷酸离子（P_4O_ <12>^<4->）与[Cp^*ticl_3]（cp^*=η^5-C_5Me_5）的反应给出[（cp^*ti）_2 _2（p_4o__4o__ <12>^<4->^<4->）使用[（cpticl）_3（μ-o）_3]导致[（cp^*ti）_3（μ-o-o）_3（p_4o_ <12>）]^ - 包含冠状形式p_4o__ <12> ligand;两种产品都具有其独特的笼子结构。另一方面，环磷酸离子（P_3O_9^<3->）的反应与[（cpticl_2）_2（μ-o）]]和[（cpticl）_3（μ-o-o）_3] [（cp^*ti）_3（μ-o）_3cl（p_3o_9）]^ - ，在这两种情况下，P_3O_3配体桥梁两个钛中心以Aη^2：η^1模式为中心。 （r = pH，^tbu）产生一系列的杂核复合物[{m（diene）} _ 4（rpo_3）_2]，其晶体学分析揭示了三种不同类型的固态结构。这些络合物在溶液中是流量的，它们的光谱分析表明，从NMR时间尺度上，四个金属片段相当。 （PPN）[RU（P_3O_9）（C_6H_6）]（PPN =（PH_3P）_2n^+）的光解在BPY（2,2'-Bipyridine）和ROH（R ​​= ME等）的情况下这些复合物在重结晶期间被氧化，以给出RU（III）或苯氧络合物（PPN）[RU（P_3O_9）（RO）（bpy）]。用环戊烯或内部炔烃处理酒精络合物会导致η^2-烷烯或η^2-Alkyne络合物，而酒精中的末端碱则可提供烷氧基碳烯络合物。

项目成果

Multimetallic Catalysis in Organic Synthesis

有机合成中的多金属催化

• 发表时间: 2004
• 作者: Sou Kamimura;Tsukasa Matsunaga;Shigeki Kuwata;Masakazu Iwasaki;Youichi Ishii;Youichi Ishii
• 通讯作者: Youichi Ishii

Syntheses, Structures, and Solution Behavior of Di- and Trinuclear Titanium(IV)-Cyclophosphato Complexes

双核和三核钛(IV)-环磷酸配合物的合成、结构和溶液行为

• 发表时间: 2004
• 期刊: Inorganic Chemistry 43
• 作者: 川口正剛;他多数;Sou Kamimura
• 通讯作者: Sou Kamimura

トリメタホスフィマト配位子を有するルテニウム,ロジウム,イリジウム錯体の構造と性質

钌、铑、铱与三偏磷配体配合物的结构和性质

• 发表时间: 2006
• 期刊: 中央大学理工学研究所論文集 11(印刷中)
• 作者: S.Kezuka;T.Okado;E.Niou;R.Takeuchi;上村 聡
• 通讯作者: 上村 聡

Structures and Properties of Ruthenium, Rhodium, and Iridium Complexes with a Trimetaphosphimato Ligand

钌、铑和铱与三偏磷配体的配合物的结构和性质

• 发表时间: 2005
• 期刊: Journal of the Institute of Science and Engineering(Chuo Univ.) 11
• 作者: Sou Kamimura;Takuya Iida;Keiichiro Kanao;Chigusa Nogawa;Yoshiaki Tanabe;Katsuyoshi Oh-ishi;Shin-ichi Fukuzawa;Youichi Ishii
• 通讯作者: Youichi Ishii

Synthesis, Structures, and Solution Behavior of Di- and Trinuclear Titanium(IV)-Cyclophosphato Complexes

双核和三核钛(IV)-环磷酸配合物的合成、结构和溶液行为

• 发表时间: 2004
• 期刊: Inorganic Chemistry 43
• 作者: Sou Kamimura;Tsukasa Matsunaga;Shigeki Kuwata;Masakazu Iwasaki;Youichi Ishii
• 通讯作者: Youichi Ishii