1997 Fiscal Year Annual Research Report

小クラスター化合物の段階的精密合成による金属-金属結合の高集積化

Research Project

Project/Area Number	08640725
Research Institution	Nara Women's University
Principal Investigator	棚瀬知明奈良女子大学, 理学部, 助教授 (50207156)
Keywords	金属クラスター / 金属-金属結合 / 3座ホスフィン / 白金錯体 / 三核錯体 / 異種金属多核錯体 / 不均一系触媒モデル / 遷移金属
Research Abstract	本研究は、立体的にデザインされた有機多座配位子を有する小クラスター化合物(金属-金属結合を持つ二核、三核錯体が中心となる)の立体構造を精密に制御し、これらを出発物質として高次クラスター骨格(三核、四核、多核)の構築を目指すことにより金属-金属結合の配列を意図的に設計しようとするものである。白金、パラジウムを中心とした二〜三核同種・異種金属クラスターの合成と構造決定および反応性について研究を行い、また、Mo(II)二核ユニットの集積にっいても検討を行った。 1 異種・同種直鎖状三核錯体の合成と構造決定-syn-[M_2(dpmp)_2(RNC)_2]^<2+>の非配位P原子の空間的配置(同方向)を利用することにより、syn体と各種単核金属錯体(M′)との反応により金属-金属結合で結ばれたM-M-M′の構造を有する三核錯体の合成とその構造決定を行った(dpmp=bis(diphenylphosphinomethyl)phenylpbosphine)。特に、白金を用いた場合にはsyn体と[Pt^0_3(RNC)_6]との反応によりside-by-sideタイプの[Pt_3(dpmp)_2(RNC)_2]^<2+>が、また、d^<10>のCu(I),Ag(I),Au(I),Pd(0),d^8のPt(II),Pd(II),Rh(I),Ir(I)等広範囲な金属を用いることにより非常に多彩なPt-Pt-M′骨格を持つ3核クラスターの合成単離に成功した。その構造は元素分析、IR、UV-visスペクトル、^1H,^<31>PNMRスペクトルさらにはX線結晶構造解析により明らかにした。また、金属-金属結合の電子状態を評価する目的で分子軌道計算を行った。これらクラスター群は固体触媒の表面モデルとして、また、新規触媒反応を開発する上で非常に重要であると考えられる。また、anti-[M_2(dpmp)_2(RNC)_2]^<2+>の非配位P原子の空間的配置(逆方向)を利用して、Pt(0),Pd(0)錯体と反応させることにより、金属-金属結合を持つAフレーム型錯体を合成し、その構造を明らかにした。この場合、加えた0価金属は三核骨格の中心に取り込まれる(M-M′-M)。 2 白金以外のBase-metalとしてMo(II),Ru(II),Pd(I)を用いdpmpによるクラスター化を試みた。Mo(II)二核錯体は単離されその構造をX線結晶解析で明らかにした。この錯体の場合、ホスフィン配位子の位置選択的酸化反応が進行する。 3 白金三核錯体[Pt_3(dpmp)_2(RNC)_2]^<2+>の有機小分子との反応を試みた結果、アルキン、アルケン、ルイス酸等が2つの共役した金属結合の一方に求電子的に付加することが明らかとなった。

Research Products

(15 results)

All Other

All Publications (15 results)

[Publications] T.Tanase,K.Ukaji,T.Igoshi et al: "Asymmetrical A-frame Triplatinum Clusters Bridged by Small Organic Molecules and Bis (diphenylphosphinomethyl) phenylphosphine" Inorganic Chemistry (American Chemical Society). 35・14. 4114-4119 (1996)
[Publications] T.Tanase,H,Toda,Y.Yamamoto: "Incorporation of Group 11 Metal Ions into Diplatinum Center Leading to Pt_2M Heterotrinuclear Complexes Supported by a Tridentate Phosphine Ligand (M=Au,Ag,Cu)" Inorganic Chemistry (American Chemical Society). 36. 1571-1577 (1997)
[Publications] 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)
[Publications] T.Tanase,T.Ohizumi et al: "Spontaneous Multiple Insertion of a Bulky Aromatic Isocyanide into the Palladium-Hydrid Bond of trans-[Pt (H) Cl (PPh_3)_2],Leading to Formation of Heterobicyclic and Pyrrole Compounds" Organometallics (American Chemical Society). 15・15. 3404-3411 (1996)
[Publications] T.Tanase,H.Toda,K.Kobayashi et al: "Platinum-Based Heterotrinuclear Complexes Involving a Group 9 Metal Ion : MCl (isocyanide)-Fragment-Capped Pt_2M T-shaped Clusters (M=Ph (I),Ir (I))" Organometallics (American Chemical Society). 15・25. 5272-5274 (1996)
[Publications] T.Tanase,H.Ukaji,Y.Yamamoto: "Dinuclear Palladium (I) Complexes with Isocyanide and N-donor Bidentate Ligands" J.Chem.Soc.Dalton Trans. (Royal Society of Chemistry). 3059-3064 (1996)
[Publications] T.Tanase,T.Aiko,Y.Yamamoto: "A Diruthenium (II) Complex Containing an Unprecedented Bridging S,O-Bidentate Dimethyl Sulfoxide Ligand" Chemical Communications (Royal Society of Chemistry). 2341-2342 (1996)
[Publications] K.Sugano,T.Tanase,Y.Yamamoto: "Formation of Heterocyclic Compounds from Reactions of Dicobalt Oxta (xylyl isocyanide) with Chloroacetone or Methyl Monochloroacetate" Journal of Organometallic Chemistry (Elsevier). 523. 197-204 (1996)
[Publications] T.Tanase,H.Takahata,H.Ukaji et al: "A-frame Trinuclear Complexes of Platinum and Palladium with a Insertion of d^<10> Pt (0) and Pd (0) Fragments into a Pt-Pt σ-Bond" Journal of Organometallic Chemistry (Elsevier). 538. 247-250 (1997)
[Publications] 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). 256. 61-67 (1997)
[Publications] 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" Inoganica Chimica Acta (Elsevier). 264. 5-9 (1997)
[Publications] T.Tanase,Y.Yamada,K.Tanaka: "Synthesis,Structures,and Spectroscopic,Magnetic,and Electrochemical Properties of M[ Ru_2 (dbpta)(μ-O_2CR)_2](M-Na and K,dbpta H_5=1,3-diamino-2-hydroxypropane tetraacetic acid)" Inorganic Chemistry (American Chemical Society). 35. 6230-6239 (1996)
[Publications] T.Tanase,H.Ukaji,H.Takahata et al: "Site-selective Incorporation of Zero-valent Platinum and Palladium Fragments into Diplatinum Centers Supported by a Triphosphine Ligand" Organometallics (American Chemical Society). 17. 196-209 (1998)
[Publications] T.Tanase,H.Toda,Y.Yamamoto: "Di-and Trinuclear Complexes of Palladium with a Triphosphine Lignad,Bis (diphenylphosphinomethyl) phenylphosphine" Journal of Organometallic Chemistry (Elsevier). (in press). (1998)
[Publications] T.Tanase,T.Inagaki,et al: "Tetranuclear Iron (III) Complexes with Amino Acids Involving a Planar (μ-Oxo)(μ-hydroxo) bis (μ-alkoxo) bis (μ-carboxylato) tetrairon Core" J.Chem.Soc.Dalton Trans. (Royal Society of Chemistry). (in press). (1998)

1997 Fiscal Year Annual Research Report

小クラスター化合物の段階的精密合成による金属-金属結合の高集積化

Principal Investigator

棚瀬 知明 奈良女子大学, 理学部, 助教授 (50207156)

Research Products

[Publications] T.Tanase,K.Ukaji,T.Igoshi et al: "Asymmetrical A-frame Triplatinum Clusters Bridged by Small Organic Molecules and Bis (diphenylphosphinomethyl) phenylphosphine" Inorganic Chemistry (American Chemical Society). 35・14. 4114-4119 (1996)

[Publications] T.Tanase,H,Toda,Y.Yamamoto: "Incorporation of Group 11 Metal Ions into Diplatinum Center Leading to Pt_2M Heterotrinuclear Complexes Supported by a Tridentate Phosphine Ligand (M=Au,Ag,Cu)" Inorganic Chemistry (American Chemical Society). 36. 1571-1577 (1997)

[Publications] 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)

[Publications] T.Tanase,T.Ohizumi et al: "Spontaneous Multiple Insertion of a Bulky Aromatic Isocyanide into the Palladium-Hydrid Bond of trans-[Pt (H) Cl (PPh_3)_2],Leading to Formation of Heterobicyclic and Pyrrole Compounds" Organometallics (American Chemical Society). 15・15. 3404-3411 (1996)

[Publications] T.Tanase,H.Toda,K.Kobayashi et al: "Platinum-Based Heterotrinuclear Complexes Involving a Group 9 Metal Ion : MCl (isocyanide)-Fragment-Capped Pt_2M T-shaped Clusters (M=Ph (I),Ir (I))" Organometallics (American Chemical Society). 15・25. 5272-5274 (1996)

[Publications] T.Tanase,H.Ukaji,Y.Yamamoto: "Dinuclear Palladium (I) Complexes with Isocyanide and N-donor Bidentate Ligands" J.Chem.Soc.Dalton Trans. (Royal Society of Chemistry). 3059-3064 (1996)

[Publications] T.Tanase,T.Aiko,Y.Yamamoto: "A Diruthenium (II) Complex Containing an Unprecedented Bridging S,O-Bidentate Dimethyl Sulfoxide Ligand" Chemical Communications (Royal Society of Chemistry). 2341-2342 (1996)

[Publications] K.Sugano,T.Tanase,Y.Yamamoto: "Formation of Heterocyclic Compounds from Reactions of Dicobalt Oxta (xylyl isocyanide) with Chloroacetone or Methyl Monochloroacetate" Journal of Organometallic Chemistry (Elsevier). 523. 197-204 (1996)

[Publications] T.Tanase,H.Takahata,H.Ukaji et al: "A-frame Trinuclear Complexes of Platinum and Palladium with a Insertion of d^<10> Pt (0) and Pd (0) Fragments into a Pt-Pt σ-Bond" Journal of Organometallic Chemistry (Elsevier). 538. 247-250 (1997)

[Publications] 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). 256. 61-67 (1997)

[Publications] 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" Inoganica Chimica Acta (Elsevier). 264. 5-9 (1997)

[Publications] T.Tanase,Y.Yamada,K.Tanaka: "Synthesis,Structures,and Spectroscopic,Magnetic,and Electrochemical Properties of M[ Ru_2 (dbpta)(μ-O_2CR)_2](M-Na and K,dbpta H_5=1,3-diamino-2-hydroxypropane tetraacetic acid)" Inorganic Chemistry (American Chemical Society). 35. 6230-6239 (1996)

[Publications] T.Tanase,H.Ukaji,H.Takahata et al: "Site-selective Incorporation of Zero-valent Platinum and Palladium Fragments into Diplatinum Centers Supported by a Triphosphine Ligand" Organometallics (American Chemical Society). 17. 196-209 (1998)

[Publications] T.Tanase,H.Toda,Y.Yamamoto: "Di-and Trinuclear Complexes of Palladium with a Triphosphine Lignad,Bis (diphenylphosphinomethyl) phenylphosphine" Journal of Organometallic Chemistry (Elsevier). (in press). (1998)

[Publications] T.Tanase,T.Inagaki,et al: "Tetranuclear Iron (III) Complexes with Amino Acids Involving a Planar (μ-Oxo)(μ-hydroxo) bis (μ-alkoxo) bis (μ-carboxylato) tetrairon Core" J.Chem.Soc.Dalton Trans. (Royal Society of Chemistry). (in press). (1998)

棚瀬知明奈良女子大学, 理学部, 助教授 (50207156)