Chemically Rational Modification of Integrated Cubane-type Frameworks

集成古巴烷型骨架的化学合理修饰

• 批准号: 02804051
• 负责人: ISOBE Kiyoshi
• 金额: $ 1.22万
• 依托单位: Okazaki National Research Institutes
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02804051/
• 关键词: Integrated Cubane-type Cluster; Triple Cubane-type; Trishomocubane-type; Quadruple Cubane-type; Partial Oxidation of Methanol; 積層立方体型クラスタ-; 四重キュバン型; メタノ-ルの部分酸化; 積層立方体型酸化物クラスタ-; 両親媒性; 有機金属基の置換

The exploitation of the reaction of the triple cubane-type cluster 1 with MeOH was undertaken to understand the heterogeneous MeOH/MoO_3 catalytic system. We found novel conversion, outlined in Scheme, of cluster 1 to trishomocubane-type cluster [(RhCp*)_2Mo_3O_9(OMe)_4](2) then to a linear quadruple cubane-type cluster [(RhCp*)_2Mo_3O_9(OMe)_4](3).The molecular structure of clusters 2 and 3 were established by single crystal X-ray analyses and characterized by IR and NMR (^1H, and ^<13>C) spectroscopy. In cluster 2 the overall conformation of methoxy and Mo=O groups gives possible model for proton and non-redox methyl transfers involved in the MeOH/MoO_3 system, and cluster 3 is a congruent representation of the layer structure of MoO_3 recovered in the catalytic cycle of partial oxidation of MeOH. The clusters described here provide a novel synthetic example of extending topological equivalent of a recognizable unit in the infinite lattice.

利用三重立方烷型簇合物1与甲醇的反应来理解非均相MeOH/MoO_3催化体系。我们发现了簇合物1转变为三均立方烷型簇合物[（RhCp*）_2Mo_3O_9（OMe）_4]（2），然后转变为线性四元立方烷型簇合物[（RhCp*）_2Mo_3O_9（OMe）_4]（3）的新颖转变过程，并通过单晶X射线分析和IR、NMR（^1H和^1C）光谱确定了簇合物2和3的分子结构<13>。簇2中的甲氧基和Mo=O基团的整体构象为MeOH/MoO_3体系中的质子和非氧化还原甲基转移提供了可能的模型，簇3是在MeOH部分氧化催化循环中回收的MoO_3的层结构的全等代表。这里描述的集群提供了一个新的合成的例子扩展拓扑等价的可识别的单元在无限晶格。

项目成果

馬越 啓介,村田 勝夫,山下 伸典,磯邉 清: "Reqctirity of 〔C^*RhP+cl_6〕(CP^*=7^5ーC_5Me_5)ーSynthesis and Structures of 〔(Cp^*Rh)_2(μーcl)_3〕〔Ptcl_5(CH_3CONH_2)〕and 〔(Cp^*Rh)_2(μーcl)_3〕_2〔Ptcl_6〕" Inorg.Chim Acta. 190. 185-191 (1991)

Keisuke Umakoshi、Katsuo Murata、Nobunori Yamashita、Kiyoshi Isobe：“〔C^*RhP+cl_6〕(CP^*=7^5－C_5Me_5)的必要性－〔(Cp^*Rh)_2(μー)的合成和结构” cl)_3]〔Ptcl_5(CH_3CONH_2)〕和〔(Cp^*Rh)_2(μーcl)_3〕_2〔Ptcl_6〕” Inorg.Chim Acta. 190. 185-191 (1991)

Youngkyudo,XiaoーZengyou,Cuiji Zhang,小澤 芳樹,磯邉 清: "TrishomocubaneーTypeMethoxide Cluster asa Novel Mediator in the Extension of Cube Size in Organometallic Oxide Cluster:Synthesis and Structure of[(RhCP^*)_2Mo_3O_9(OMe)_4]・MeOH and a Linear Quadruple Cubaneー

Youngkyudo、Xiao-Zengyou、Cuiji Zhang、Yoshiki Ozawa、Kiyoshi Isobe：“三甲基立方烷型甲氧化物簇作为有机金属氧化物簇中立方尺寸扩展的新型介体：[(RhCP^*)_2Mo_3O_9(OMe)_4]的合成和结构・MeOH和线性四重古巴烷ー

小澤 芳樹,林 宜仁,磯邊 清: "Structure of Triammonium Hexahydrogen hexamolybdro-rhodata(III)Hexahydrate" Acta Cryst.C47. 637-638 (1991)

Yoshiki Ozawa、Yoshihito Hayashi、Kiyoshi Isobe：“六氢三铵六钼钼（III）六水合物的结构”Acta Cryst.C47（1991）。

K. Umakoshi, K. Murata, S. Yamashita, and K. Isobe: "Reactivity of [Cp*RhPtCl_6 (Cp*=eta^5-C_5Me_5). Synthesis and Structures of [Cp*Rh)_2(mu-Cl)_3[PtCl_5(CH_3CONH_2)] and [(Cp*Rh)_2(mu-Cl)_3]_2[PtCl_6]" Inorg. Chim. Acta. 190. 185 (1991)

K. Umakoshi、K. Murata、S. Yamashita 和 K. Isobe：“[Cp*RhPtCl_6 (Cp*=eta^5-C_5Me_5) 的反应性。[Cp*Rh)_2(mu-Cl) 的合成和结构”

林 宜仁,小澤 芳樹,磯邉 清: "Site Selective OxygenーExchange and Substitution of Organomelallic Group in Amphilic AuadrupleーCubabane Type Cluster.Synthesis and Molecular Structure of 〔(MCp)_4V_6O_<19>〕(M=Rh,Ir)" Inorg,Chem,. 30. 1025-1033 (1991)

Yoshihito Hayashi、Yoshiki Ozawa、Kiyoshi Isobe：“位点选择性氧－两亲性四元体－古巴烷型簇中有机金属基团的交换和取代。[(MCp)_4V_6O_<19>](M=Rh,Ir)的合成和分子结构”无机化学，30。1025-1033（1991）