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Assembly of metal-metal bonds through small-size clusters

Assembly of metal-metal bonds through small-size clusters
通过小尺寸簇组装金属-金属键
批准号:
08640725
负责人:
TANASE Tomoaki
金额:
$1.41万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
1996
资助国家:
日本
项目状态:
已结题
起止时间:
1996 至 1997

项目摘要

项目成果

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中文摘要
翻译
金属-金属键合的铂和钯的小尺寸簇作为非均相催化剂表面的最小模型越来越引起人们的兴趣;结构、性质和反应性可以通过改变合成策略和有机配体的选择来改变。报道了以双铂为前驱体,以双(二苯基膦- m -乙基)苯基膦(dpmp)为原料系统合成同源和杂三金属铂簇。[Pt_2(RNC)_6]^<2+> (RNC=芳香族异氰化物)与dpmp反应得到了顺-反-[Pt_2(dpmp)_2(RNC)_2]^<2+> (syn-1和anti-2)的异构体混合物。syn-1和反-2的不同反应性允许获得多用途的homo和hetero三核团簇聚集。前(syn-1)改变了治疗Pt ^ 0, Pt ^ <二>,Pd ^ 0, Pd ^ <二>,Rh ^我,红外^我,非盟^我Ag) ^我和铜^我物种多种Pt-Pt-M集群、线性- [Pt_2 (dpmp) _2 (RNC) _2) ^ < 2 + > (M = Pt, Pd), asym-A-frame - [Pt_2MCl_2 (dpmp) _2 (RNC) _2) ^ < 2 + > (M = Pt, Pd), t形——[Pt_2MCl (dpmp) _2 (RNC) _2) ^ < 2 + > (M = Ir, Rh),人字形- [Pt_2M (dpmp) _2 (RNC) _2) ^ < 3 + > (M =盟,Ag)和菱形- [Pt_2CuX (dpmp) _2] ^ < 2 + > (X = Cl, Br,我)。配合anti-2与Pt^0和Pd^0处理得到Pt-Pt-Pt和Pt-Pd-Pt a -框架簇。有趣的是,额外金属的插入位置是由两个不协调的磷化氢单位1和2的排列来调节的。还制备了二核和三核铂钼配合物,并对其进行了表征。
英文摘要
Metal-metal bonded small-size clusters of platinum and palladium have been of increasing interest as minimal models for the surface of heterogeneous catalysts ; structures, properties, and reactivities are able to be modified by varying the synthetic strategy and the choice of organic ligands. Systematic syntheses of homo- and heterotrimetallic platinum clusters through diplatinum precursors with bis (diphenylphosphino m ethyl) phenyl phosphine (dpmp) are reported. The reaction of [Pt_2(RNC)_6]^<2+> (RNC=aromatic isocyanide) with dpmp afforded an isomeric mixture of syn- and anti-[Pt_2(dpmp)_2(RNC)_2]^<2+> (syn-1 and anti-2). The differential reactivity of syn-1 and anti-2 allows an access to versatile aggregations of homo and hetero trinuclear clusters. The former (syn-1) was transformed by treatment with Pt^0, Pt^<II>, Pd^0, Pd^<II>, Rh^I, Ir^I, Au^I, Ag^I, and Cu^I species to a wide variety of Pt-Pt-M clusters, linear-[Pt_2(dpmp)_2(RNC)_2]^<2+> (M=Pt, Pd), asym-A-frame-[Pt_2MCl_2(dpmp)_2(RNC)_2]^<2+> (M=Pt, Pd), T-shape-[Pt_2MCl(dpmp)_2(RNC)_2]^<2+> (M=Ir, Rh), Y-shape-[Pt_2M(dpmp)_2(RNC)_2]^<3+> (M=Au, Ag), and rhombic-[Pt_2CuX(dpmp)_2]^<2+> (X=Cl, Br, I). Treatment of complex anti-2 with Pt^0 and Pd^0 species gave Pt-Pt-Pt and Pt-Pd-Pt A-frame clusters. The inserted position of an additional metal was interestingly regulated by the arrangements of two uncordinate phosphine units of 1 and 2. Di- and trinuclear plladium and molybdenum complexes with dpmp were also prepared and characterized.
期刊论文(56)
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会议论文
T.Tanase,T.Igoshi,Y.Yamamoto: "Synthesis and Characterization of Quadruply Bonded Dinucelar Molybdenum(II)Complexes with Bis(diphenylphosphinomethyl)phenylphosphine and Oxidation of the Triphosphine Ligand" Inorganica Chimica Acta(Elsevier). (in press). (
T.Tanase、T.Igoshi、Y.Yamamoto:“四键双环钼 (II) 与双(二苯基膦甲基)苯基膦配合物的合成和表征以及三膦配体的氧化”Inorganica Chimica Acta(Elsevier)。
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T.Tanase,H.Takahata,Y.Yamamoto: "Zero-valent Group 10 Metal Complexes with a Triphosphine Ligand,[M(dpmp)2],where M=Pt,Pd,Ni,and dpmp=bis(diphenylphosphinomethyl)phenylphosphine" Inorganica Chimica Acta(Elsevier). (in press). (1997)
T.Tanase、H.Takahata、Y.Yamamoto:“具有三膦配体的零价第 10 族金属络合物,[M(dpmp)2],其中 M=Pt、Pd、Ni,且 dpmp=双(二苯基膦甲基)苯基膦
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T.Tanase, Y.Yamamoto, et al: "[{Pt (diphosphine) (isocyanide)}_2Pt]^<2+> Recharacterized as[{Pt (diphosphine) (isocyanide)}_2Hg]^<2+>" Organometallics (American Chemical Society). 15・5. 1502-1504 (1996)
T.Tanase、Y.Yamamoto 等人:“[{Pt (二膦)(异氰化物)}_2Pt]^<2+> 重新表征为[{Pt (二膦)(异氰化物)}_2Hg]^<2+>”有机金属化合物(美国化学会)15・5。
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T.Tanase, T.Ohizumi et al: "Spontaneous Multiple Insertion of a Bulky Aromatic Isocyanide into the Palladium-Hydrid Bond of trans- [Pd (H) Cl (PPh_3)_2],Leading to Formation of Heterobicyclic and Pyrrole Compounds" Organometallics (American Chemical Socie
T.Tanase、T.Ohizumi 等人:“将大量芳香族异氰化物自发多重插入反式 [Pd (H) Cl (PPh_3)_2] 的钯-氢化物键,导致形成杂双环和吡咯化合物”
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共 56 条
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