Development of Structurally Constrained Metal Clusters Leading to Functional Nano-Molecular Devices

结构约束金属簇的开发导致功能纳米分子器件

• 批准号: 13304053
• 负责人: TANASE Tomoaki
• 金额: $ 34.94万
• 依托单位: Nara Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13304053/
• 关键词: Metal Cluster; Metal-metal Bond; Hexanuclear Complex; Platinum; Tridentate Phosphine; Bisisocyanide; Quantum Wire; Nano-structured Molecule

Linear transition-metal clusters have recently attracted increasing attention concerning their unique structural, optical, and electrochemical properties. Attempts to build up much expanded molecules with multi-functional metal-metal interactions are highly desired in relation to development of molecular-based electronic devices as well as to exploration of unprecedented physical and chemical behaviors. In this project, we have studied the syntheses, characterization, and reactivities of linear hexanuclear clusters. Reduction of Pt_3 complex 1 with NaBH_4 in E_tOH afforded the linear hexaplatinum cluster, [Pt_6(μ-H)(μ-dpmp)_4(RNC)_2(PF_6)_3 (3), whereas the analogous heterometallic cluster, [Pt_4Pd_2(μ-H)(μ-dpmp)_4(RNC)_2](PF_6)_3 (4), was synthesized from reaction of Pt_2Pd complex 2 with NaOMe ([PL_2M(μ-dpmp)_2(RNC)_2](PF_6)_2 (M=Pt (1), Pd (2); dpmp=bis(diphenyl- phosphinomethyl)phenylphosphine, RNC=organoisocyanide). Complex 3a (R=Xyl) is a trivalent, 86e-cluster and involves a linear Pt_6 core (Pt-Pt(central)=3.3092(5) Å, Pt-Pt(inner)=av. 2.733 Å, Pt-Pt(outer)= av. 2.704 Å) supported by four dpmp ligands and terminally coordinated by two isonitriles. The clusters 3a and 4a readily underwent two-electron oxidation to afford [Pt_4Pd_2(μ-dpmp)_4(RNC)_2](PP_6)_4 (M=Pt (5a), Pd (5b)). Reduction of 1 with NaBH_4 in DMF afforded dark green trihydride hexaplatinum complex, [Pt_6(μ-H)(H)_2(μ-dpmp)_4](PF_6) which was interestingly converted into neutral hexplatinum cluster with coordinatively unsaturated terminals, [Pt_6(μ-H)_2(μ-dpmp)_4] (6). The trihydride cluster readily reacted with Mel to give [Pt_6(μ-H)(I)_2(μ-dpmp)_4](PF_6). These linear clusters with hydrides could be of significant importance as reactive functional metal wires coupled with redox processes. The SAM's (self assembled monolayer) of bisisocyanide-linked 3a were prepared and characterized by electrochemical methods.

线型过渡金属团簇由于其独特的结构、光学和电化学性质，近年来引起了人们越来越多的关注。随着基于分子的电子器件的发展以及对前所未有的物理和化学行为的探索，人们非常希望建立具有多功能金属-金属相互作用的扩展分子。在这个项目中，我们研究了线性六核簇合物的合成、表征和反应性。用NaBH_4在E_TOH中还原铂配合物1得到六铂簇合物[Pt_6(μ-H)(μ-DPMP)_4(Rnc)_2(PF_6)_3(3)]，而类似的异金属簇合物[PT_4Pd_2(μ-H)(μ-dpMP)_4(Rnc)_2](PF_6)_3(4)，[Pl_2m(μ-DPMP)_2(Rnc)_2](Pf_6)_2(M=铂(1)，钯(2)；DPMP=二(二苯基膦甲基)苯基膦，RNC=有机异氰化物)。配合物3a(R=XYL)是一个三价的86e-簇合物，并且包括一个线性的Pt6核心(Pt6中心)=3.3092(5)Å，PtPlt(内部)=av。2.733Å，铂-铂(外部)=av。2.704Å)由四个dpmp配体支撑并由两个异腈末端配位。簇合物3a和4a易发生双电子氧化反应生成[Pt4Pd2(μ-dpmp)4(Rnc)2](PP6)4(M=Pt(5a)，Pd(5b))。在DMF中用NaBH4还原1得到了深绿色的三氢化合六铂配合物[Pt6(μ-H)(H)2(μ-dpmp)4](Pf6)，它有趣地转化为末端配位不饱和的中性六铂簇合物[Pt6(μ-H)2(μ-dpmp)4](6)。三氢化物团簇很容易与MEL反应生成[Pt6(μ-H)(I)2(μ-dpmp)4](Pf6)。这些带有氢化物的线性团簇作为反应功能金属丝与氧化还原过程相结合可能具有重要意义。制备了双异氰酸酯3a自组装单分子膜，并用电化学方法对其进行了表征。

项目成果

T.Tanase, M.Hamaguchi et al.: "Cyclic Dimerization of Tetracyanoethylene Promoted on Linear Triplatinum Centres Leading to Novel Nitrene-Bridged Pt_3 Complexes"Chem. Commun. (Royal Society of Chemistry). 1072-1073 (2001)

T.Tanase、M.Hamaguchi 等人：“线性三铂中心上促进的四氰乙烯的环状二聚化导致新型氮烯桥 Pt_3 复合物”Chem。

Cage-type Hexanuclear Platinum(0) Clusters with Diphosphine and Isocyanide Ligands Encapsulatine Two Mercury(0) Atoms

含有二膦和异氰化物配体的笼型六核铂(0)团簇封装两个汞(0)原子

• 发表时间: 2005
• 期刊: Organometallics (American Chemical Society) 24
• 作者: T.Tanase;E.Goto et al.
• 通讯作者: E.Goto et al.

Cyclic Dimerization of Tetracyanoethylene Promoted on Linear Triplatinum Centers Leading to Novel Nitrene-Bridged Pt_3 Complexes

线性三铂中心上四氰乙烯的环状二聚反应产生新型氮烯桥 Pt_3 配合物

• 发表时间: 2001
• 期刊: Chem.Commun.(Royal Society of Chemistry)
• 作者: T.Tanase;M.Hamaguchi et al.
• 通讯作者: M.Hamaguchi et al.

Linear, redox-active Pt6 and Pt2Pd2Pt2 clusters.

• DOI: 10.1002/anie.200460707
• 发表时间: 2004-09
• 期刊: Angewandte Chemie
• 作者: Eri Goto;R. Begum;Shu-zhong Zhan;T. Tanase;K. Tanigaki;K. Sakai

T.Tanase: "Recent Development of Linearly Ordered Multinuclear Transition-Metal Complexes (Accounts)"Bull. Chem. Soc. Jpn. (Chemical Society of Japan). (in press). (2002)

T.Tanase：“线性有序多核过渡金属配合物的最新进展（记录）”公牛。