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.

我们发现利用环磷酸根离子和Cp^*Ti单元，环四磷酸根离子(P_4O_<12>^<4->)与[Cp^*TiCl_3](Cp)反应可以合成一系列有机金属笼配合物。 ^*=η^5-C_5Me_5) 给出[(Cp^*Ti)_2(P_4O_<12>^<4->)_2]^<2-> 其中 P_4O_<12> 配体采用鞍形构象，而 [(CpTiCl)_3(μ-O )_3] 导致 [(Cp^*Ti)_3(μ-O)_3(P_4O_<12>)]^- 包含冠形P_4O_<12>配体；两种产物均具有独特的笼结构；另一方面，环三磷酸根离子(P_3O_9^<3->)与[(CpTiCl_2)_2(μ-O)]和[(CpTiCl)的反应。 _3(μ-O)_3] 得到 [(Cp^*Ti)_2(μ-O)(P_3O_9)_3]^<2-> 和分别为 [(Cp^*Ti)_3(μ-O)_3Cl(P_3O_9)]^-，并且在两种情况下，P_3O_3 配体以 η^2:η^1 模式桥接两个钛中心。我们还表明[M(MeO)(二烯)]_2 (M=Rh,Ir) 与有机膦酸酯 RPO_3H_2 (R=Ph,^tBu) 反应生成一系列双核配合物 [{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，这些配合物在溶液中是流动的，并且它们的光谱分析表明这四种金属碎片是等效的。从羟基磷灰石负载钌分子模型的角度详细研究了钌环三磷酸配合物的反应活性(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) 存在下的光解。提供醇或酚络合物 (PPN)[Ru(P_3O_9)(ROH)(bpy)] 这些络合物在过程中被氧化。重结晶得到 Ru(III) 烷氧基或苯氧基络合物 (PPN)[Ru(P_3O_9)(RO)(bpy)] 用环戊烯或内炔处理醇络合物得到 η^2-烯烃或 η^2 -炔配合物，而在醇中与末端炔配合物则提供烷氧基卡宾配合物。

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