2001 Fiscal Year Annual Research Report

斬新な配位子の設計とそれらを利用した新規高配位有機ヘテロ元素化合物の創製

Research Project

Project/Area Number	12304037
Research Institution	The University of Tokyo
Principal Investigator	川島隆幸東京大学, 大学院・理学系研究科, 教授 (80011766)
Co-Investigator(Kenkyū-buntansha)	狩野直和東京大学, 大学院・理学系研究科, 助手 (00302810) 後藤敬東京大学, 大学院・理学系研究科, 講師 (70262144)
Keywords	デンドリマー型置換基 / m-テルフェニルユニット / 5配位ジフルオロシリカート / 5配位トリフルオロシリカート / X線結晶構造解析 / 三方両錐構造
Research Abstract	m-テルフェニルユニットを基盤とするデンドリマー型置換基の開発と5配位ケイ素化合物の合成については、まず、1,3,5-トリブロモ-2-ヨードベンゼンに2-ブロモ-1, 3-ジメチルベンゼンから調製したグリニヤール試薬を反応させ、臭化2,2",6,6"-テトラメチル-m-テルフェニル-5'-イル(DenBr)を合成した。次に、DenBrをt-BuLiと反応させ、リチオ化した後、テトラクロロシランと反応させ、Den_4Siを合成した。これに、トリフルオロメタンスルホン酸を作用させた後、加水分解することで、シラノールDen_3SiOHを得た。これを塩化アセチルと反応させ、相当するクロロシランDen_3SiClに変換した。このクロロシランとフッ素化剤(NH_4)_2SiF_6からDen_3SiFを得た。このフルオロシランにトルエン中、[2.2.2]cryptand存在下、KFと作用させることで相当する5配位ジフルオロシリカートの生成を確認した。しかし、得られた単結晶のX線結晶構造解析から、化合物はトリフルオロシリカートであることが分かり、再結晶中、Den基がフッ化物イオンにより置換されたものと考えられる。トリフルオロシリカートは二つのフッ素原子がアピカル位を占め、二つのDen基とフッ素原子がエクアトリアルを占めた三方両錐構造をとっていることが分かった。また、カリウムカチオンはcryptand内になく、エクアトリアル位のフッ素と相互作用しているという興味ある結果が得られた。

Research Products
(24 results)

All Other

All Publications (24 results)

[Publications] J.Kobayashi: "Synthesis, Structure and Bonding Properties of 5-Carbaphosphatranes : A New Class of Main Group Atranes"J. Am. Chem. Soc.. 124(in press). (2002)
[Publications] N.Kano: "Cycloaddition Reactions of an Iminophosphorane Bearing the Martin Ligand with Some Double-Bond Compounds : Syntheses, Structures and Thermolyses of a 1,3,2λ^5-Oxazaphosphetidine and a 1,3,2λ^5-Diazaphosphetidine-4-thione"Polyhedron. 21(in press). (2002)
[Publications] S.Sase: "Fluoride Ion Abstraction of Phosphonium Cations from Their Counter Anion : A Novel Synthetic Method of Fluorophosphoranes"Chem. Lett.. (in press). (2002)
[Publications] N.Kano: "Synthesis of Four- and Five-membered Heterocycles Derived from an Iminophosphorane"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)
[Publications] J.Kobayashi: "Reactions of 1-Hydro-5-carbaphosphatrane : Tautomerization between Five Coordinate and Three Coordinate Species"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)
[Publications] K.Goto: "Bonding Properties of 5-Carbaphosphatranes"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)
[Publications] S.Sase: "Novel Synthetic Method of Fluorophosphoranes by Fluoride Ion Abstraction from Tetrafluoroborate"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)
[Publications] S.Sase: "Synthesis of the First Stable Pentacoordinate Selenaphosphirane"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)
[Publications] K.Goto: "Synthesis of Novel Triarylphosphines Bearing a m-Terphenyl-based Dendrimer-type Framework"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)
[Publications] K.Saruhashi: "Structural Characterization of a Pentacoordinate Monohydrosilane with the Appical Si-H Bond"Chem. Heterocyclic Compounds. 1524-1525 (2001)
[Publications] K.Goto: "The First Synthesis of a Stable Selenenic Acid by Direct Oxidation of a Selenol : Experimental Demonstration of Three Processes Induced in the Catalytic Cycle of Glutathione Peroxidase"Org. Lett.. 3. 3569-3572 (2001)
[Publications] K.Goto: "Synthesis, Structure, and Reactions of a Novel Triarylsilanol with a Bowl-type Framework : A Silanol Extremely Resistant to Self-condensation"Chem. Lett.. 1258-1259 (2001)
[Publications] K.Goto: "Synthesis, Structure, and Reactions of the First stable Aromtic S-Nitorosothiol Bearing a Novel Dendrimer-type Steric Protecting Group"Chem. Lett.. 1204-1205 (2001)
[Publications] N.Kano: "The First Isolable Pentacoordinate 1,2λ^5-Azaphosphetine : Synthesis, X-ray Crystallographic Analysis, and Dynamic Behaviour"Chem. Commun.. 2096-2097 (2001)
[Publications] N.Kano: "Reversible Photo-Control of the Coordination Number of Silicon in a Tetrafluorosilicate Bearing a 2-(Phenylazo)phenyl Group"J. Am. Chem. Soc.. 123. 10778-10779 (2001)
[Publications] K.Naganuma: "Synthesis and Structure of the First Pentacoordinate Thiasiliranides"J. Orgnaomet. Chem.. 643-644. 504-507 (2001)
[Publications] N.Kano: "A Disilane Containing Two Heptacoordinate Silicon Atoms : Synthesis and Structure of a Disilane Bearing Dithiocarboxylato Ligands"Angew. Chem., Int. Ed.. 40. 3450-3452 (2001)
[Publications] N.Kano: "Novel Ring System with a Se-O-N Linkage : Synthesis and Crystal Structure of the First 1,2λ^4,5-Oxaselenazolidine"Chem. Lett.. 610-611 (2001)
[Publications] Y.Uchiyama: "Synthesis and Structure of a Novel Ladder Type Organobismuth Compounds with Bismuth-Oxygen Interactions"Organometallics. 20. 2440-2442 (2001)
[Publications] J.Kobayashi: "Synthesis and Structure of 5-Carbaphosphatrane"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 597-600 (2001)
[Publications] N.Kano: "Synthesis and Thermolysis of the Novel Ring Systems Containing Nitrogen and Tetracoordinate Selenium"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 259-262 (2001)
[Publications] T.Kawashima: "Synthesis and Structure of a Tricoodinate 1,2-Iodoxetane"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 141-144 (2001)
[Publications] N.Kano: "Synthesis and Structures of Azobenzenes Bearing Silyl, Germyl, and Stannyl Groups at 2-Position"Chem. Lett.. 338-339 (2001)
[Publications] T.Kawashima: "Phosphorus-Carbon Heterocyclic Chemstry : The Rise of a New Domain"Pergamon. 61 (2001)

2001 Fiscal Year Annual Research Report

斬新な配位子の設計とそれらを利用した新規高配位有機ヘテロ元素化合物の創製

Principal Investigator

川島 隆幸 東京大学, 大学院・理学系研究科, 教授 (80011766)

Research Products

[Publications] J.Kobayashi: "Synthesis, Structure and Bonding Properties of 5-Carbaphosphatranes : A New Class of Main Group Atranes"J. Am. Chem. Soc.. 124(in press). (2002)

[Publications] N.Kano: "Cycloaddition Reactions of an Iminophosphorane Bearing the Martin Ligand with Some Double-Bond Compounds : Syntheses, Structures and Thermolyses of a 1,3,2λ^5-Oxazaphosphetidine and a 1,3,2λ^5-Diazaphosphetidine-4-thione"Polyhedron. 21(in press). (2002)

[Publications] S.Sase: "Fluoride Ion Abstraction of Phosphonium Cations from Their Counter Anion : A Novel Synthetic Method of Fluorophosphoranes"Chem. Lett.. (in press). (2002)

[Publications] N.Kano: "Synthesis of Four- and Five-membered Heterocycles Derived from an Iminophosphorane"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

[Publications] J.Kobayashi: "Reactions of 1-Hydro-5-carbaphosphatrane : Tautomerization between Five Coordinate and Three Coordinate Species"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

[Publications] K.Goto: "Bonding Properties of 5-Carbaphosphatranes"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

[Publications] S.Sase: "Novel Synthetic Method of Fluorophosphoranes by Fluoride Ion Abstraction from Tetrafluoroborate"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

[Publications] S.Sase: "Synthesis of the First Stable Pentacoordinate Selenaphosphirane"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

[Publications] K.Goto: "Synthesis of Novel Triarylphosphines Bearing a m-Terphenyl-based Dendrimer-type Framework"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

[Publications] K.Saruhashi: "Structural Characterization of a Pentacoordinate Monohydrosilane with the Appical Si-H Bond"Chem. Heterocyclic Compounds. 1524-1525 (2001)

[Publications] K.Goto: "The First Synthesis of a Stable Selenenic Acid by Direct Oxidation of a Selenol : Experimental Demonstration of Three Processes Induced in the Catalytic Cycle of Glutathione Peroxidase"Org. Lett.. 3. 3569-3572 (2001)

[Publications] K.Goto: "Synthesis, Structure, and Reactions of a Novel Triarylsilanol with a Bowl-type Framework : A Silanol Extremely Resistant to Self-condensation"Chem. Lett.. 1258-1259 (2001)

[Publications] K.Goto: "Synthesis, Structure, and Reactions of the First stable Aromtic S-Nitorosothiol Bearing a Novel Dendrimer-type Steric Protecting Group"Chem. Lett.. 1204-1205 (2001)

[Publications] N.Kano: "The First Isolable Pentacoordinate 1,2λ^5-Azaphosphetine : Synthesis, X-ray Crystallographic Analysis, and Dynamic Behaviour"Chem. Commun.. 2096-2097 (2001)

[Publications] N.Kano: "Reversible Photo-Control of the Coordination Number of Silicon in a Tetrafluorosilicate Bearing a 2-(Phenylazo)phenyl Group"J. Am. Chem. Soc.. 123. 10778-10779 (2001)

[Publications] K.Naganuma: "Synthesis and Structure of the First Pentacoordinate Thiasiliranides"J. Orgnaomet. Chem.. 643-644. 504-507 (2001)

[Publications] N.Kano: "A Disilane Containing Two Heptacoordinate Silicon Atoms : Synthesis and Structure of a Disilane Bearing Dithiocarboxylato Ligands"Angew. Chem., Int. Ed.. 40. 3450-3452 (2001)

[Publications] N.Kano: "Novel Ring System with a Se-O-N Linkage : Synthesis and Crystal Structure of the First 1,2λ^4,5-Oxaselenazolidine"Chem. Lett.. 610-611 (2001)

[Publications] Y.Uchiyama: "Synthesis and Structure of a Novel Ladder Type Organobismuth Compounds with Bismuth-Oxygen Interactions"Organometallics. 20. 2440-2442 (2001)

[Publications] J.Kobayashi: "Synthesis and Structure of 5-Carbaphosphatrane"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 597-600 (2001)

[Publications] N.Kano: "Synthesis and Thermolysis of the Novel Ring Systems Containing Nitrogen and Tetracoordinate Selenium"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 259-262 (2001)

[Publications] T.Kawashima: "Synthesis and Structure of a Tricoodinate 1,2-Iodoxetane"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 141-144 (2001)

[Publications] N.Kano: "Synthesis and Structures of Azobenzenes Bearing Silyl, Germyl, and Stannyl Groups at 2-Position"Chem. Lett.. 338-339 (2001)

[Publications] T.Kawashima: "Phosphorus-Carbon Heterocyclic Chemstry : The Rise of a New Domain"Pergamon. 61 (2001)

川島隆幸東京大学, 大学院・理学系研究科, 教授 (80011766)