1999 Fiscal Year Annual Research Report

典型元素-遷移金属間結合の化学

Research Project

Project/Area Number	09239105
Research Institution	Osaka City University
Principal Investigator	小澤文幸大阪市立大学, 工学部, 教授 (40134837)
Co-Investigator(Kenkyū-buntansha)	宮浦憲夫北海道大学, 大学院・工学研究科, 教授 (10002049) 巽和行名古屋大学, 物質科学国際研究センター, 教授 (10155096) 榊茂好熊本大学, 工学部, 教授 (20094013) 小坂田耕太郎東京工業大学, 資源化学研究所, 教授 (00152455) 飛田博実東北大学, 大学院・理学研究科, 助教授 (30180160)
Keywords	ボウ素 / ケイ素 / ゲルマニウム / スズ / リン / イオウ / 遷移金属 / 錯体
Research Abstract	[小澤文幸](1)白金及びルテニウム錯体上での炭素-ケイ素結合形成反応機構を系統的に研究し、ケイ素位子に特徴的な反応を明らかにした。(2)シリル(スタイル)白金錯体とフェニルアセチレンとの反応における選択因子を明らかにした。[榊茂好】(1)パラジウム錯体におけるπ-アリル基と含14族元素配因子との還元的脱離反応について理論的研究を行った。(2)パラジウムとボリル、シリル、ゲルミルあるいはスタニル基との結合エネルギーを理論的に評価するとともに、これらの置換基間のインターエレメント結合の酸化的付加反応について検討した。[巽和行](1)6族遷移金属-カルコゲニド多重結合をもつ一連の錯体の合成に成功した。(2)新規トリスルフィド錯体を構成単位とする一連の高次異核金属クラスターを構築できた。[宮浦憲夫](1)遷移金属触媒を用いるシボロンのクロスカップリング反応について系統的に研究した。(2)シボロンが高い結合角歪みを有するメチレンシクロプロパンに付加反応を行うことを見出した。[桑田博実]鉄-ケイ素-リンおよび鉄-ケイ素-カルコゲンからなる新しい三員環メタラサイクルを合成した。また、これらの化合物とピリジンまたはケトン類との反応によって五員環および七員環メタラサイクルをそれぞれ合成できた。生成したメタラサイクルはいずれも鉄-ケイ素間に不飽和結合性をもつ。[小坂田耕太郎]含硫黄及び含ケイ素有機配位子の金属間移動反応を検討した。いくつかの二核金属錯体が得られ、それらの研究によって金属間シリル基移動反応機構に関する知見が得られた。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] F. Ozawa: "Reactions of bis (silyl) palladium (II) cpmplexes with allyl halides. Synthesis of mono (silyl) palladium (II) halides and X-ray structure of trans PdCL(SiF_2Ph) (Pme_2PH)_2"Inorg. chim. Acta. 296. 19-25 (1999)
[Publications] F. Ozawa: "A New Process for C-Si Bond Formation from cis-Alkyl (silyl) platinum(II) Complexes"Chem. Lett.. (12). 1289-1290 (1999)
[Publications] F. Ozawa: "Insertion of Phenylacetylene into cis-Silyl (stannyl) platinum Complexes"Chem. Lett.. (12). 1307-1308 (1999)
[Publications] Y. Maruyama: "Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium (II) Complexes with Hydrosilanes"Organometallics. 19(印刷中). (2000)
[Publications] K. Hasebe: "Thermolysis Reactions of cis-PtR (SiPH^3) (Pme_2PH)_2 in Solution"Organometallics. 19(印刷中). (2000)
[Publications] Y. Maruyama: "Hydrosilylation of 1,4-bis (trimethylsilyl)-l-buten-3-ynes using late transition metal hydrides as catalyst precursors"J. Organomet. Chem. (印刷中). (2000)
[Publications] B. Biswas: "Theoretical Study of the Structure, Bonding Nature, and Reductive Elimination Reaction of Pd (XH_3) (η^3-C_3H_5)(PH _3)(X=C, Si, Ge, Sn)"Organometallics. 18. 4015-4026 (1999)
[Publications] S. Sakaki: "Theoretical Study on σ-Bond Activation of (HO)_2 B-XH_3 by M (PH_3)_2(X=C, Si, Ge, or Sn; M=Pd or Pt)"Organometallics. 18. 4825-4837 (1999)
[Publications] S. Sakaki: "Pt-catalyzed hydrosillylation of ethylene. A theoretical study of the reaction mechanism"Coord. Che m. Rev.. 190-192. 933-960 (1999)
[Publications] J.-P. Lang: "Aggregation of the Half-sandwich Trisulfido Complex of Tungsten with Silver Ions : Synthesis of Cyanide-bridged Helical Polymer"Irorg. Chem.. 38. 1364-1367 (1999)
[Publications] Y. Arikawa: "Synthesis of Bis {2-dimethylphosphino) ethane-l-thiolato} bis (t-butylthiolato) - Molybdenum (IV) and Its Cluster Forming Reactions with FeCl_2and CuBr"Irorg. Chem.. 38. 4549-4553 (1999)
[Publications] J-P. Lang: "Novel W/Cu/S Cluster Compounds Derived from [PPh_4][η^5-C_5Me_5(WS_3] : Synthesis and Structures of a Triple Incomplete Cubane Cluster"Chem. Commun. 2315-2316 (1999)
[Publications] K. Takahashi: "Synthesis of l-Alkenylboronic Esters via Palladium-catalyzed Cross-coupling Reaction of Bis (pinacolato) diboron with l-Alkenyl Halides and Triflates"Chem. Lett.. 126-127 (2000)
[Publications] T. Ishiyama: "Platinum (0)-Catalyzed Diboration of Methylenecyclopropanes with Bis (pinacolato)- diboron : A Selective Route to 2,4-Bis (boryl)-l-butenes"Synlett.. 1790-1792 (1999)
[Publications] H. Tobita: "Extremely Facile Arene Exchange on a Ruthenium (II) Complex Having a Novel Bis (silyl) Chelata Ligand (9,9-Dimethylxanthene-4,5-diyl) bis (dimethylsilyl) (Xantsil)"Organometallics. 18. 2058 (1999)
[Publications] K. Kuge: "Synthesis and Structures of Heterometallic Clusters [CpFe (CO)_2]_2(μ^3-S_2W (CO)_5and Cp_2Fe_2 (CO)_2(μ CO) W^3-S) W (CO)_5 and Kinetic Study of Migration Study of Migration"Chem, Commun.. (12). 1061-1062 (1999)
[Publications] Y. -J. Kim: "Dipalladiium Complexes with Bridigng Diorganosilye Ligands. Synthesis, Structures, and Properties of [Lpd (μ-SiH (R) Ph)]_2(R=Ph, Me ; L=Pme_3, Pet_3,PMePh_2"J. Chem. Soc, Delton Trans.. (3). 417-422 (2000)
[Publications] K, Osakada: "Mechanistic Features of Intermoleculae Thiolato Ligands Trasfer from Thiolatotitanocene to Pt (Cl) Me (cod) To Give Methyl (arylthiolato) platinum (II) Complexes"Bull. Chem. Soc. Jpn. 73(印刷中). (2000)

1999 Fiscal Year Annual Research Report

典型元素-遷移金属間結合の化学

Principal Investigator

小澤 文幸 大阪市立大学, 工学部, 教授 (40134837)

Research Products

[Publications] F. Ozawa: "Reactions of bis (silyl) palladium (II) cpmplexes with allyl halides. Synthesis of mono (silyl) palladium (II) halides and X-ray structure of trans PdCL(SiF_2Ph) (Pme_2PH)_2"Inorg. chim. Acta. 296. 19-25 (1999)

[Publications] F. Ozawa: "A New Process for C-Si Bond Formation from cis-Alkyl (silyl) platinum(II) Complexes"Chem. Lett.. (12). 1289-1290 (1999)

[Publications] F. Ozawa: "Insertion of Phenylacetylene into cis-Silyl (stannyl) platinum Complexes"Chem. Lett.. (12). 1307-1308 (1999)

[Publications] Y. Maruyama: "Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium (II) Complexes with Hydrosilanes"Organometallics. 19(印刷中). (2000)

[Publications] K. Hasebe: "Thermolysis Reactions of cis-PtR (SiPH^3) (Pme_2PH)_2 in Solution"Organometallics. 19(印刷中). (2000)

[Publications] Y. Maruyama: "Hydrosilylation of 1,4-bis (trimethylsilyl)-l-buten-3-ynes using late transition metal hydrides as catalyst precursors"J. Organomet. Chem. (印刷中). (2000)

[Publications] B. Biswas: "Theoretical Study of the Structure, Bonding Nature, and Reductive Elimination Reaction of Pd (XH_3) (η^3-C_3H_5)(PH _3)(X=C, Si, Ge, Sn)"Organometallics. 18. 4015-4026 (1999)

[Publications] S. Sakaki: "Theoretical Study on σ-Bond Activation of (HO)_2 B-XH_3 by M (PH_3)_2(X=C, Si, Ge, or Sn; M=Pd or Pt)"Organometallics. 18. 4825-4837 (1999)

[Publications] S. Sakaki: "Pt-catalyzed hydrosillylation of ethylene. A theoretical study of the reaction mechanism"Coord. Che m. Rev.. 190-192. 933-960 (1999)

[Publications] J.-P. Lang: "Aggregation of the Half-sandwich Trisulfido Complex of Tungsten with Silver Ions : Synthesis of Cyanide-bridged Helical Polymer"Irorg. Chem.. 38. 1364-1367 (1999)

[Publications] Y. Arikawa: "Synthesis of Bis {2-dimethylphosphino) ethane-l-thiolato} bis (t-butylthiolato) - Molybdenum (IV) and Its Cluster Forming Reactions with FeCl_2and CuBr"Irorg. Chem.. 38. 4549-4553 (1999)

[Publications] J-P. Lang: "Novel W/Cu/S Cluster Compounds Derived from [PPh_4][η^5-C_5Me_5(WS_3] : Synthesis and Structures of a Triple Incomplete Cubane Cluster"Chem. Commun. 2315-2316 (1999)

[Publications] K. Takahashi: "Synthesis of l-Alkenylboronic Esters via Palladium-catalyzed Cross-coupling Reaction of Bis (pinacolato) diboron with l-Alkenyl Halides and Triflates"Chem. Lett.. 126-127 (2000)

[Publications] T. Ishiyama: "Platinum (0)-Catalyzed Diboration of Methylenecyclopropanes with Bis (pinacolato)- diboron : A Selective Route to 2,4-Bis (boryl)-l-butenes"Synlett.. 1790-1792 (1999)

[Publications] H. Tobita: "Extremely Facile Arene Exchange on a Ruthenium (II) Complex Having a Novel Bis (silyl) Chelata Ligand (9,9-Dimethylxanthene-4,5-diyl) bis (dimethylsilyl) (Xantsil)"Organometallics. 18. 2058 (1999)

[Publications] K. Kuge: "Synthesis and Structures of Heterometallic Clusters [CpFe (CO)_2]_2(μ^3-S_2W (CO)_5and Cp_2Fe_2 (CO)_2(μ CO) W^3-S) W (CO)_5 and Kinetic Study of Migration Study of Migration"Chem, Commun.. (12). 1061-1062 (1999)

[Publications] Y. -J. Kim: "Dipalladiium Complexes with Bridigng Diorganosilye Ligands. Synthesis, Structures, and Properties of [Lpd (μ-SiH (R) Ph)]_2(R=Ph, Me ; L=Pme_3, Pet_3,PMePh_2"J. Chem. Soc, Delton Trans.. (3). 417-422 (2000)

[Publications] K, Osakada: "Mechanistic Features of Intermoleculae Thiolato Ligands Trasfer from Thiolatotitanocene to Pt (Cl) Me (cod) To Give Methyl (arylthiolato) platinum (II) Complexes"Bull. Chem. Soc. Jpn. 73(印刷中). (2000)

小澤文幸大阪市立大学, 工学部, 教授 (40134837)