Architecture and properties of platinum group metal cluster complexes bearing polydentate ligands

带有多齿配体的铂族金属簇配合物的结构和性能

• 批准号: 09640677
• 负责人: YAMAMOTO Yasuhiro
• 金额: $ 2.05万
• 依托单位: Toho University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640677/
• 关键词: Platinum; triphosphine; trinuclear complexes; Isocyanide; nitrosyl; 1, 1-Bis(diphenylphosphino)ferroce; Hietero nuclear; Patladium; Triphosphine; Plalinum; Heteronuclear complex; A-frame complex; Linear complex; Tridentate Phosplune; Group l

Reaction of diplatinum complexes 1 bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp), [PtィイD22ィエD2(dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 with M(RNC)ィイD22ィエD2 (M = Pt or Pd) underwent insertion of the metal fragment into a Pt-Pt bond to give homo- or heterotrinuclear A-frame complexes [PtィイD22ィエD2MX(dpmp)ィイD22ィエD2(RNC)ィイD24ィエD2]ィイD12+ィエD1. When complex 1 was treated with group 11 metal ions, the metal ions were incorporated into a diplatinum center to give [PtィイD22ィエD2M(dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD13+ィエD1 (M = Au, Ag) or [PtィイD22ィエD2MX(dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 (M = Cu ; X = Cl, Br, I) (Scheme 1). In the ィイD131ィエD1P{ィイD11ィエD1H} nmr spectra of Pt-Cu mixed complexes the chemical shifts was related with halogens. Trinuclear complex [PtィイD23ィエD2(dpmp)ィイD22ィエD2(RNC)ィイD24ィエD2]ィイD12+ィエD1 reacted readily with [NO][BFィイD24ィエD2] to yield unprecedented nitrosyl-bridged double A-frame complexes, [PtィイD23ィエD2(dpmp)ィイD22ィエD2(NO)(RNC)ィイD22ィエD2]ィイD14+ィエD1. Dinuclear palladium complexes, [PdィイD22ィエD2(dppf)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 were prepared from the reaction of [PdィイD22ィエD2(RNC)ィイD24ィエD2]ィイD12+ィエD1 with 1, 1'-bis(diphenylphosphino)ferrocene (dppf). The photochemical reactions of these complexes led to cleavage of a Pd-Pd bond.Our research on platinum and palladium complexes bearing triphosphine have been reported : Trends in Organometallic Chemistry, 35-69 (1999).

双铂配合物1的反应（二苯基膦基甲基）苯基膦（DPMP），[铂酰D22铂酰D2（dpmp）铂酰D22铂酰D2（RNC）铂酰D22铂酰D2]铂酰D12+铂酰D1与M（RNC）铂酰D22铂酰D2（dpmp）铂酰D22铂酰D2（RNC）铂酰D22铂酰D2]铂酰D12+铂酰D1与M（RNC）铂酰D22铂酰D2（RNC）铂酰D22铂酰D2（RNC）铂酰D22铂酰D2]铂酰D12+铂酰D1与M（RNC）铂酰D22铂酰D2（M = Pt或Pd）进行金属片段插入到Pt-Pt键中，得到同或异三核A-框架配合物[Pt <$D22 <$D2MX（dpmp）<$D22 <$D2（RNC）RC24 RC2] RC12 + RC1。当用第11族金属离子处理配合物1时，金属离子被引入双铂中心，得到[Pt D22 D2 M（dpmp）D22 D2（RNC）D22 D2] D13+ D1（M = Au，Ag）或[Pt（Pt）2-D22-D2MX（dpmp）2-D22-D2MX（RNC）2-D22-D2] 2-D12+ Pt（Pt）2-D1（M = Cu ; X = Cl，Br，I）（方案1）。在Pt-Cu混配合物的X射线D131 X射线D1 P {X射线D11 X射线D1 H}核磁共振谱中，化学位移与卤素有关。三核配合物[Pt <$D23 <$D2（dpmp）<$D22 <$D2（RNC）<$D24 <$D2]<$D12 +<$D1很容易与[NO][BF <$D24 <$D2]反应，得到前所未有的亚硝酰基桥连双A框架配合物[Pt <$D23 <$D2（dpmp）<$D22 <$D2（NO）（RNC）<$D22 <$D2]<$D14 +<$D1。由[Pd（Ⅱ）D22（Ⅱ）D24（Ⅱ）D2][Pd（Ⅱ）D22（Ⅱ）D24（Ⅱ）D2][Pd（Ⅱ）D22（Ⅱ）D24（Ⅱ）D2][Pd（Ⅱ）D12 + Pd（Ⅱ）D1]与1，1 '-二（二苯基膦基）二茂铁（dppf）反应，合成了双核钯配合物[Pd（Ⅱ）D22（Ⅱ）D2（Ⅱ）D2（RNC）D22（Ⅱ）D2][Pd（Ⅱ）D12+ Pd（Ⅱ）D1]。我们对带有三膦的铂和钯络合物的研究已经报道：Trends in Organisms Chemistry，35-69（1999）。

项目成果

山本ら: "Site-selective ineaporation of zevovalent platinum fragments of into diplatinum centered supported by a triphosphine ligard"Organomefallics. 17. 196-209 (1998)

Yamamoto 等人：“Zevovalent 铂片段的位点选择性蒸发成以三膦配体为中心的二铂”Organomefallics 17. 196-209 (1998)。

Y.Yamamoto, et al.: "A-Frame trinuclear complexes of platinum and palladium with a A-Frame trinuclear complexes of platinum and palladium with a tridentate phosphine ligand. Insertion of dィイD110ィエD1tridentate Pt and Pd(0) atoms into Pt-Pt σ-bond."J.Organo

Y. Yamamoto 等人：“铂和钯的 A 型三核配合物以及具有三齿膦配体的铂和钯的 A 型三核配合物。将二D110D1 三齿 Pt 和 Pd(0) 原子插入 Pt-Pt σ -邦德。”J.Organo

山本ら: "Dimoly bdenum complexes with a potentially tetradentate PNP ligard, 2-7-bis Cdiphemylphino)-1.8naphthyridine"J. chem. Research(6). 538-539 (1998)

Yamamoto 等人：“二钼 bdenum 与潜在四齿 PNP 配体 2-7-bis Cdiphemylphino)-1.8naphthyridine 的配合物”J. chem Research(6)。

Y.Yamamoto, et al.: "Unprecedented nitrosyl-bridged double-A-frame triplatinum complexes, [PtィイD23ィエD2(μ-tri phosphine)ィイD22ィエD2(μ-NO)ィイD22ィエD2(RNC)ィイD22ィエD2](BFィイD24ィエD2)ィイD24ィエD2"Chem Comm.. 745-746 (1999)

Y. Yamamoto 等人：“前所未有的亚硝基桥接双 A 架三铂复合物，Chem Comm.. 745-746 (1999)

山本ら: "Unprecedented nitrosyl-bridged double-A-frame triplatinum complexes [Pt_3(μ-triphosphine)_2(b-NO)_2(RNC)_2](BF_4)_4"J. chem. Soc. Chem. Commun.. 745-746 (1999)

Yamamoto 等人：“前所未有的亚硝酰桥双 A 框架三铂配合物 [Pt_3(μ-三膦)_2(b-NO)_2(RNC)_2](BF_4)_4”J. Commun. ..745-746 (1999)