Synthesis and Regulated Functions of Multinuclear Transition Metal Complexes Based on Tetranuclear Palladium and Platinum Complexes

• Project/Area Number: 19205008
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: OSAKADA Kohtaro Tokyo Institute of Technology, 資源化学研究所, 教授 (00152455)
• Co-Investigator(Kenkyū-buntansha): 田邊 真 東京工業大学, 資源化学研究所, 助教 (80376962) ; 須崎 裕司 東京工業大学, 資源化学研究所, 助教 (70436707)
• Project Period (FY): 2007 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥48,360,000 (Direct Cost: ¥37,200,000、Indirect Cost: ¥11,160,000); Fiscal Year 2010: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2009: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000); Fiscal Year 2008: ¥13,130,000 (Direct Cost: ¥10,100,000、Indirect Cost: ¥3,030,000); Fiscal Year 2007: ¥19,370,000 (Direct Cost: ¥14,900,000、Indirect Cost: ¥4,470,000)
• Keywords: パラジウム / 白金 / 多核錯体 / ケイ素配位子 / 平面構造 / パラジム / 二次元機能 / 金属間結合 / 小分子活性化 / クラスター / 有機ケイ素配位子

Research Abstract

A number of tetranuclear complexes of Pd and Pt containing the bridging Si and Ge ligands were prepared. The synthetic reactions proceeds smoothly and recversibly, and are revealed to show high generality. The tetranucelar complexes react with CuI and AgI to afford hetero-pentanuclear complexes and with thiol to produce the linear tetrapalladium complexes or hexanuclear palladium complexes.

Research Products

• [Journal Article] 1, 4-Hydrosilation of Pyridine by Ru Catalyst.A New Reaction and Mechanism (2011)
  • Author(s): K.Osakada
  • Journal Title: Angew.Chem., Int.Ed. in press.
  • Peer Reviewed
• [Journal Article] Chemical Properties of Tetragermaplatinacyclopentane. Inser-tion of an Alkyne into a Pt-Ge Bond and Silylation Caused by H_2SiPh_2 (2011)
  • Author(s): M.Tanabe, T.Deguchi, K.Osakada
  • Journal Title: Organometallics. in press.
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Platinasilsesquioxane Complexes and their Reaction with Arylboronic Acid (2011)
  • Author(s): N.Mintcheva, M.Tanabe, K.Osakada
  • Journal Title: Organometallics 30 Pages: 187-190
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Platinasilsesquioxane Complexes and their Reaction with Arylboronic Acid (2011)
  • Author(s): N.Mintcheva, M.Tanabe, K.Osakada
  • Journal Title: Organometallics Volume: 30 Pages: 187-190
  • Peer Reviewed
• [Journal Article] Preparation and Reactivity of an O, O-Chelating Silsesquioxane-Palladium Complex (2011)
  • Author(s): M.Tanabe, K.Mutou, N.Mintcheva, K.Osakada
  • Journal Title: Jourmal of Organometallic Chemistry Volume: 696 Pages: 1211-2151
  • Peer Reviewed
• [Journal Article] Chemical Properties of Dinuclear Pd and Pt Complexes with Bridging Silylene Ligands. Use of (Aminosily)boranes as a Precursor of the Silylene (2011)
  • Author(s): M.Tanabe, J.Jiang, H.Yamazawa K.Osakada, T.Ohmura, M.Suginome
  • Journal Title: Organometallics Volume: 30(印刷中)
  • Peer Reviewed
• [Journal Article] 1, 4-Hydrosilylation of Pyridine by Ru Catalyst. A New Reaction and Mechanism (2011)
  • Author(s): K.Osakada
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50(印刷中)
  • Peer Reviewed
• [Journal Article] Ge-Ge Bond-Forming Reactions from Bis(germyl)palladium Complexes with Chelating Diphosphine Ligands (2011)
  • Author(s): M.Tanabe, M.Hanzawa, K.Osakada
  • Journal Title: Phosphorus, Sulfur, and Silicon and the Related Elements Volume: (印刷中)
  • Peer Reviewed
• [Journal Article] Sila-and Germametallacycles of Late Transition Metals (2010)
  • Author(s): M.Tanabe, K.Osakada
  • Journal Title: Organometallics 29 Pages: 4702-4710
  • Peer Reviewed
• [Journal Article] Preparation and Thermal Reaction of Tetrastanna-palla-dacyclopentane.Sn-Sn Bond Formation and Cleavage (2010)
  • Author(s): M.Tanabe, M.Hanzawa, K.Osakada
  • Journal Title: Organometallics 29 Pages: 3535-3540
  • Peer Reviewed
• [Journal Article] Sila-and Germametallacycles of Late Transition Metals (2010)
  • Author(s): M. Tanabe, K.Osakada
  • Journal Title: Organometallics Volume: 29 Pages: 4702-4710
  • Peer Reviewed
• [Journal Article] Preparation and Thermal Reaction of Tetrastannapalladacyclopentane. Sn-Sn Bond Formation and Cleavage (2010)
  • Author(s): M.Tanabe, M.Hanzawa, K.Osakada
  • Journal Title: Organometallics Volume: 29 Pages: 3535-3540
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of a Dinuclear Platinum Complex with Silsesquioxanate Ligand (2010)
  • Author(s): N.Mintcheva, M.Tanabe, K.Osakada, I.Georgieva, T.Mihailov, N.Trendafilova
  • Journal Title: Jourmal of Organometallics Chemistry Volume: 695 Pages: 1738-1743
  • Peer Reviewed
• [Journal Article] Formation and Ring Expansion of Germaplatinacycles via Dehydrogenative Ge-Ge and Ge-Pt Bond-forming Reaction (2009)
  • Author(s): M.Tanabe, M.Hanzawa, N.Ishikawa, K.Osakada
  • Journal Title: Organometallics 28 Pages: 6014-6019
  • Peer Reviewed
• [Journal Article] Reaction of Isocyanides with a Molybdenum Complex Containing a Tridentate Silyl Ligand (2009)
  • Author(s): M.Minato, G.Kikutsuji, M.Kakeya, K.Osakada, M.Yamasaki
  • Journal Title: Dalton Trans. Pages: 7684-7687
  • Peer Reviewed
• [Journal Article] Planar Tetranuclear and Dumbbell-shaped Octanuclear Pd Complexes with Bridging Silylene Ligands (2009)
  • Author(s): T.Yamada, A.Mawatari, M.Tanabe, K.Osakada, T.Tanase
  • Journal Title: Angew.Chem., Int.Ed. 48 Pages: 568-571
  • Peer Reviewed
• [Journal Article] Planar Tetranuclear and Dumbbell-shaped Octanuclear Pd Complexes with Bridging Silylene Ligands (2009)
  • Author(s): Tetsuyuki Yamada, Akane Mawatari, Makoto Tanabe, Kohtaro Osakada, Tomoaki Tanase
  • Journal Title: Angew. Chem., Int. Ed. 48 Pages: 568-571
  • Peer Reviewed
• [Journal Article] Formation and Ring Expansion of Germaplatinacycles via Dehydrogenative Ge-Ge and Ge-Pt Bond-Forming Reactions (2009)
  • Author(s): Makoto Tanabe, Masaya Hanzawa, Naoko Ishikawa, Kohtaro Osakada
  • Journal Title: Organometallics 28 Pages: 6014-6019
  • Peer Reviewed
• [Journal Article] Formation and Ring Expansion of Germaplatinacycles via Dehydrogenative Ge-Ge and Ge-Pt Bond-Forming Reactions (2009)
  • Author(s): M.Tanabe, M.Hanzawa, N.Ishikawa, K.Osakada
  • Journal Title: Organometallics 28 Pages: 6014-6019
  • Peer Reviewed
• [Journal Article] Reaction of Isocyanides with a Molybdenum Comples Containing a Tridentate Silyl-phosphine Ligand : the Si Ligand Effeet on Site preference of the Isociyanide Ligands (2009)
  • Author(s): M.Minato, G.Kikutsuiji, M.Kakeya, K.Osakada, M.Yamasaki
  • Journal Title: Dalton Trans. Pages: 7684-7687
  • Peer Reviewed
• [Journal Article] Dialkyl-and diaryl-platinum (II) complexes with secondary phosphines. Preparation, structure and thermal reaction giving the metallopolymer (2009)
  • Author(s): M.Kakeya, M.Tanabe, Y.Nakamura, K.Osakada
  • Journal Title: J.Organomet.Chem. 694 Pages: 2270-2278
  • Peer Reviewed
• [Journal Article] Planar Tetranuclear and Dumbbell-shaped Octanuclear Pd Complexes with Bridging Silylene Ligands (2009)
  • Author(s): Yamada, T., Mawatari, A., Tanabe, M., Osakada, K., Tanase, T.
  • Journal Title: Angew. Chem., Int. Ed. 48 Pages: 568-571
  • Peer Reviewed
• [Journal Article] Mono-and Dinuclear Germapalladacycles Obtained via the Ge-Ge Bond Forming Reactions Promoted by Pd Complexes (2008)
  • Author(s): M.Tanabe, N.Ishikawa, M.Hanzawa, K.Osakada
  • Journal Title: Organometallics 27 Pages: 5152-5158
  • Peer Reviewed
• [Journal Article] Ligand Exchange of Diplatinum Complexes with Bridging Silyl Ligands Involving Si-H Bond Cleavage and Formation (2008)
  • Author(s): M.Tanabe, D.Ito, K.Osakada
  • Journal Title: Organometallics 27 Pages: 2258-2267
  • Peer Reviewed
• [Journal Article] Preparation and NMR Studies of Palladium Complexes with a Silsesquioxanate Ligand (2008)
  • Author(s): M.Tanabe, K.Mutou, N.Mintcheva, K.Osakada
  • Journal Title: Organometallics 27 Pages: 519-523
  • Peer Reviewed
• [Journal Article] Ligand Exchange of Diplatinum Complexes with Bridging Silyl Ligands Involving Si-H Bond Cleavage and Formation (2008)
  • Author(s): Makoto Tanabe, Daisuke Ito, Kohtaro Osakada
  • Journal Title: Organometallics 27 Pages: 2258-2267
  • Peer Reviewed
• [Journal Article] Mono- and Dinuclear Germapalladacycles Obtained via the Ge-Ge Bond Forming Reactions Promoted by Pd Complexes (2008)
  • Author(s): Tanabe, M., Ishikawa, N., Hanzawa, M., Osakada, K.
  • Journal Title: Organometallics 27 Pages: 5152-5158
  • Peer Reviewed
• [Journal Article] Ligand Exchange of Diplatinum Complexes with Bridging Silyl Ligands Involving Si-H Bond Cleavage and Formation (2008)
  • Author(s): Tanabe. M, Ito, D, Osakada, K.
  • Journal Title: Organometallics 27 Pages: 2258-2267
  • Peer Reviewed
• [Journal Article] Preparation and NMR Studies of Palladium Complexes with a Silsesquio xanate Ligand (2008)
  • Author(s): Makoto Tanabe, Kohji Mutou, Neli Mintcheva, Kohtaro Osakada
  • Journal Title: Organometallics 27(印刷中)
  • Peer Reviewed
• [Journal Article] Dipalladium Complex with Bridging Silylene Ligands, [{Pd(dmpe)}_2(μ-SiPh_2)_2], Formed via Dimerization of Bis(silyl)Pd Complex (2007)
  • Author(s): M.Tanabe, A.Mawatari, K.Osakada
  • Journal Title: Organometallics 26 Pages: 2937-2940
  • Peer Reviewed
• [Journal Article] Arylpalladium Complexes with a Silsesquioxanate Ligand. Preparation and Structures in Solid State and Solution (2007)
  • Author(s): N.Mintcheva, M.Tanabe, K.Osakada
  • Journal Title: Organometallics 26 Pages: 1402-1410
  • Peer Reviewed
• [Journal Article] Dipalladium Complex with Bridging Silylene Ligands, [{Pd(dmpe)}_2(μ-SiPh_2)_2], Formed via Dimerization of Bis (silyl) palladium Complex (2007)
  • Author(s): Makoto Tanabe, Akane Mawatari, Kohtaro Osakada
  • Journal Title: Organometallics 26 Pages: 2937-2940
  • Peer Reviewed
• [Journal Article] Dipalladium Complex with Bridging Silylene Ligands, [{Pd(dmpe)}_2(μ-SiPh_2)_2], Formed via Dimerization of Bis(silyl)palladium Complex (2007)
  • Author(s): Makoto Tanabe, Akane Mawatari, Kohtaro Osakada
  • Journal Title: Organometallics 26 Pages: 2937-2940
  • Peer Reviewed
• [Journal Article] Arylpalladium Complexes with a Silsesquioxanate Ligand. Preparation and Structures in Solid State and in Solution (2007)
  • Author(s): Neli Mintcheva, Makoto Tanabe Kohtaro Osakada
  • Journal Title: Organometallics 26 Pages: 1402-1410
  • Peer Reviewed
• [Presentation] シリレン移動反応によるパラジウム, 白金錯体の合成 (2010)
  • Author(s): 蒋健, 田邊真, 小坂田耕太郎, 大村智通, 杉野目道紀
  • Organizer: 第14回ケイ素化学協会シンポジウム
  • Place of Presentation: ニューウェルシティ湯河原
  • Year and Date: 2010-11-18
• [Presentation] 平面構造Pd_4Ge_3錯体による結合活性化と変換反応 (2010)
  • Author(s): 千葉舞, 田邊真, 小坂田耕太郎
  • Organizer: 第14回ケイ素化学協会シンポジウム
  • Place of Presentation: ニューウェルシティ湯河原
  • Year and Date: 2010-11-18
• [Presentation] ケイ素で橋架けする平面構造Pt, Pd錯体の特異な元素配列 (2010)
  • Author(s): 湯本遼平, 田邊真, 小坂田耕太郎
  • Organizer: 第14回ケイ素化学協会シンポジウム
  • Place of Presentation: ニューウェルシティ湯河原
  • Year and Date: 2010-11-18
• [Presentation] Preparation and Structure of Planar Hexagonal Pd-Pt Complexes with Bridging Silylene Ligands (2010)
  • Author(s): 田邊真、湯本遼平、小坂田耕太郎
  • Organizer: The 3^<rd> Asian Silicon Symposium
  • Place of Presentation: 中国杭州
  • Year and Date: 2010-10-19
• [Presentation] Preparation and Structure of Planar Hexagonal Pd-Pt Complexes with Bridging Silylene Ligands (2010)
  • Author(s): Makoto Tanabe, Ryouhei Yumoto, Kohtaro Osakada
  • Organizer: The 3^<rd> Asian Silicon Symposium
  • Place of Presentation: 杭州(中国)
  • Year and Date: 2010-10-19
• [Presentation] Silylene Transfer Reaction of (Aminosily)boronic Esters Activated by Platinum Complex (2010)
  • Author(s): Jian Jiang, Makoto Tanabe, Kohtaro Osakada
  • Organizer: The 3^<rd> Asian Silicon Symposium
  • Place of Presentation: 杭州(中国)
  • Year and Date: 2010-10-19
• [Presentation] 鎖状構造ゲルミレン-パラジウム多核錯体の合成と性質 (2010)
  • Author(s): 千葉舞, 石川尚子, 半沢公也, 田邊真, 小坂田耕太郎
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: 大阪国際交流センター
  • Year and Date: 2010-09-27
• [Presentation] 白金含有環状オリゴゲルマン錯体の合成 (2010)
  • Author(s): 出口尚史, 半沢公也, 田邊真, 小坂田耕太郎
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: 大阪国際交流センター
  • Year and Date: 2010-09-27
• [Presentation] 平面構造PtPd_3を核とする多金属錯体の効率的合成と構造評価 (2010)
  • Author(s): 湯本遼平, 山田哲行, 田邊真, 小坂田耕太郎
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: 大阪国際交流センター
  • Year and Date: 2010-09-27
• [Presentation] 14族元素-遷移金属で構成される新構造多核錯体の合成と元素配列変換 (2010)
  • Author(s): 田邊真, 福田智子, 湯本遼平、千葉舞, 小坂田耕太郎
  • Organizer: 第57回有機金属討論会
  • Place of Presentation: 中央大学
  • Year and Date: 2010-09-17
• [Presentation] 14族元素-遷移金属で構成される新構造多核錯体の合成と元素配列変換 (2010)
  • Author(s): 田邊真、福田智子、湯本遼平、千葉舞、小坂田耕太郎
  • Organizer: 第57回有機金属討論会
  • Place of Presentation: 東京、首都大
  • Year and Date: 2010-09-16
• [Presentation] Tetrapalladium Complexes with Bridging Silylene Ligands. New Structures and Properties (2010)
  • Author(s): 小坂田耕太郎、田邊真
  • Organizer: 43^<rd> Silicon Symposium
  • Place of Presentation: 米国、セントルイス(招待講演)
  • Year and Date: 2010-05-22
• [Presentation] Tetrapalladium Complexes with Bridging Silylene Ligands. New Structures and Properties" (2010)
  • Author(s): Kohtaro Osakada, Makoto Tanabe
  • Organizer: 43^<rd> Silicon Symposium (invited)
  • Place of Presentation: St Louis (USA)
  • Year and Date: 2010-05-22
• [Presentation] 含金属ゲルマサイクルを鍵とする平面構造パラジウム四核錯体の合成と可逆的を構造変換 (2009)
  • Author(s): 半沢公也, 石川尚子, 田邉真, 小坂田耕太郎
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学 文教キャンパス
  • Year and Date: 2009-09-25
• [Presentation] 有機Si、Ge配位子をもつ有機遷移金属錯体 (2008)
  • Author(s): 小坂田耕太郎
  • Organizer: 日本化学会第2回関東支部大会
  • Place of Presentation: 桐生、群馬大学(招待講演)
  • Year and Date: 2008-09-18
• [Presentation] 有機ケイ素、ゲルマニウム配位子をもっ有機遷移金属錯体 (2008)
  • Author(s): 小坂田耕太郎
  • Organizer: 日本化学会第2回関東支部大会(招待講演)
  • Place of Presentation: 群馬大学, 桐生
  • Year and Date: 2008-09-18
• [Presentation] Hexagonal Tetrapalladium Clusters with Bridging Silylene or Germylene Ligands (2007)
  • Author(s): 田邊真、石川尚子、馬渡あかね、小坂田耕太郎
  • Organizer: XVIII EuCheMS Conference on Organometallic Chemistry
  • Place of Presentation: ブルガリア、ソフィア
  • Year and Date: 2007-09-03
• [Presentation] Hexagonal Tetrapalladium Clusters with Bridging Silylene or Germylene Ligands (2007)
  • Author(s): Makoto Tanabe, Naoko Ishikawa, Akane Mawatari, Kohtaro Osakada
  • Organizer: XVIII EuCheMS Conference on Organometallic Chemistry
  • Place of Presentation: Sofia (Bulgaria)
  • Year and Date: 2007-09-03
• [Book] 「典型元素-遷移金属錯体の化学」、現代化学増刊44, 「有機金属化学の最前線-多様な元素を使いこなす-」 (2011)
  • Author(s): 小板田耕太郎、飛田博実
  • Publisher: 東京化学同人
• [Book] 有機金属化学(錯体化学会選書 6)(中沢、小坂田編) (2010)
  • Publisher: 三共出版
• [Remarks] ホームページ
  • URL: http://www.res.titech.ac.jp/~shinkin/