1998 Fiscal Year Annual Research Report

比較元素論的14族元素低配位活性種の構造と反応性

Research Project

Project/Area Number	10894021
Research Institution	Tohoku University
Principal Investigator	吉良満夫東北大学, 大学院・理学研究科, 教授 (40004452)
Co-Investigator(Kenkyū-buntansha)	平塚浩士群馬大学, 工学部, 教授 (00016156) 松本英之群馬大学, 工学部, 教授 (90008467) 関口章筑波大学, 化学系, 教授 (90143164) 坂本健吉東北大学, 大学院・理学研究科, 助教授 (50187035) 萩野博東北大学, 大学院・理学研究科, 教授 (00004292)
Keywords	比較元素論 / 14族元素活性種 / 14族元素不飽和分子
Research Abstract	本研究課題では将来の特定領域研究への展開を意図して、カルベン、ラジカル、イオンなどの有機活性種とその14族金属類縁体の構造、物性、反応性の比較研究の動向を分担して研究調査することを目的とした。シリレン、ゲルミレン、スタンニレンおよびプルンビレンの生成、構造と反応性の研究を櫻井、荻野、中平、吉良、持田、時任、赤阪が担当し、これまでのカルベン化学に関する知識の集積および最近の沢木、富岡らの炭素の2価化学種に関する研究成果と比較して、元素間の構造と反応性の類似性と相違性を系統的に研究した。シリルラジカルの分光を平塚が、安定ケイ素およびゲルマニウムラジカルの単離、構造と反応性の研究を松本が行い、炭素ラジカルとの差異を比較した。14族元素カチオンの単離および構造と反応性の研究を関口が行い、竹内、園田らのカルボカチオンに関する先端的研究の成果と比較した。同様の観点からシリルおよびゲルミルアニオンの化学(河内)、14族有機金属分子のラジカルイオンの化学(水野)、14族金属不飽和化学種のシラエテン(坂本、石川、九内)、ジシレンおよびシラベンゼン(時任)に関する研究調査を行った。また、非経験的分子軌道法を用いたケイ素-ケイ素3重結合分子の構造の理論的考察を永瀬が研究調査した。上記の研究結果を総合的に議論する会議を開催し、有機活性種に関する構造論と物性論の現状とその限界を活発に討論し、この様なアプローチを広範囲に展開して将来特定領域研究の新しい研究領域に発展させるべきであるとの共通認識に達した。

Research Products

(33 results)

All Other

All Publications (33 results)

[Publications] T.Iwamoto: "Bimolecular reactions of tetrakis(trialkylsilyl)disilenes with various reagents" Bull.Chem.Soc.Jpn.71. 2741-2747 (1998)
[Publications] T.Iwamoto: "The First Stable Cyclotrisilene" J.Am.Chem.Soc.121(4). 886-887 (1999)
[Publications] H.Ogino: "Bridged silylene and germylene complexes" Adv.Organomet.Chem.42. 224-290 (1998)
[Publications] H.Tobita: "Synthesis and properties of intramolecularly base-stabilized disilany(silylene)ruthenium and-iron complexes" Organometallics. 17. 2850-2856 (1998)
[Publications] T.Veszpremi: "An ab initio MO study of structure and reactivity of 4-silatriafulvene" J.Am.Chem.Soc.120(10). 2408-2414 (1998)
[Publications] S.Tsutsui: "Bis(diisopropylamino)silylene and its dimer" J.Am.Chem.Soc.120(38). 9955-9956 (1998)
[Publications] M.Ichinohe: "Synthesis and Structure of Cyclotrigemenium Salt of the Tetrakis{3,5-bis(trifluoromethyl)phenyl}borate Anion,A Stable Free Germyl Cation in the Condensed Phase" Chem.Lett.1045-1046 (1998)
[Publications] S.Kyushin: "Highly Planar Silane[(i-Pr)3Si]3SiH and Silyl Radical[(i-Pr)3Si]3Si" Chem.Lett.2. 107-108 (1998)
[Publications] T.Yoshinaga: "Solid Surface Enhancement Effects on Chemiluminescence.II.Diaryloxalate and Polymers as Media Solids" J.Lumin.78. 221-229 (1998)
[Publications] M.Taguchi: "Chemical Tracks of Heavy Ions for 1,2,4,5-Tetracyanobenzen Anion Radical Formation" Nucl.Instrum.Meth.B. 134. 427-430 (1998)
[Publications] T.Sanji: "Highly Selective Mono-and Polyallylation of polychlorosilanes and Polyshlorodisilanes^1" Organometallics. 17(23). 5068-5071 (1998)
[Publications] D.Sasaki: "Optical characteristics of ultrathin oligosilane films prepared by molecular beam deposition method" Jpn.J.Appl.Phys.37. 953-955 (1998)
[Publications] K.Mochida: "Radical Anions of Oligogermanes,Me(Me2Ge)nMe(n=2,3,5,10)Generated by Pulse Radiolysis" Chem.Lett.2263-2264 (1998)
[Publications] K.Mochida: "Radical Cation of Dedecamethylcyclohexagermane Generated by Pulse Radiolysis" Chem.Lett.3-4 (1999)
[Publications] T.Akasaka: "Photochemical Bissilylation of C60 with Disilane" J.Org.Chem.64. 566-569 (1999)
[Publications] H.Yokoi: "In-Cage Formation of Carbanions in Photoinduced Electron-Transfer Reaction of Carboxylate Ions" J.Am,Chem.Soc.120. 12453-12458 (1998)
[Publications] H.Tomioka: "Persistent High-Spin Polycarbene.Generation of Polybrominated Tris-1,3,5-[4-(phenylcarbeno)-phenylethynyl]benzene(S=3)and Spin Identification by 2D Electron Spin Transient Nutation(2D-ESTN)Spectroscopy)" J.Am.Chem.Soc.120. 1106-1107 (1998)
[Publications] S.Murata: "Photochemistry of 2,4-Bis(diazo)-1,2,3,4-tetrahydronaphthalene-1,3-dione:Selective Photodecomposition of One of the Two Inequivatent Diazo Groups" J.Am.Chem.Soc.120. 9088-9089 (1998)
[Publications] Y.Yoshimi: "A Novel Photorearrangement of Aryl Naphthylemethyl Ethers.Formation of Cyclohexa-2,4-dienone Derivatives" Tetrahedron Lett.39. 4683-4686 (1998)
[Publications] K.Mizuno: "A Novel Intramolecular photocyclization of 2-(4,5-Dimethyl-2-oxa-4-hexenyl)-1-methoxycarbonylnaphthalene via 1,9-Hydrogen Abstraction" Chem.Commun.1659-1660 (1998)
[Publications] K.Tokunaga: "Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:Evaluation of π Conjugative Stabilization of α-Thiocarbonyl Carbocations" J.Org.Chem.63(7). 2209-2217 (1998)
[Publications] Y.Tanaka: "Self-Condensation Reaction of Lithium(Alkoxy)silylenoid:A Model Study by ab Initio Calculation" Organometallics. 17(21). 4573-4577 (1998)
[Publications] A.Kawachi: "Reaction of{Tris[2-(dimethylamino)phenyl]germyl}lithium with Elemental Selenium:Formation of 2,2,4,4-Tetrakis[2-(dimethylamino)phenyl]-1,3,2,4-diselenadigermetane" Chem.Lett.1. 21-22 (1999)
[Publications] A.Naka: "The reactions of tris(trimethylsiyl)silyllithium with ketenes" J.Organomet.Chem.(印刷中).
[Publications] A.Naka: "Synthesis and Platinum-and Palladium-Catalyzed Reactions of Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene)" Organometallics. 17(26). 5830-5835 (1998)
[Publications] J.Ohshita: "Synthesis and Properties of Dithienosiloles" J.Organomet.Chem.553. 487-491 (1998)
[Publications] J.Ohshita: "Polymeric Organosilicon Systems.XXIX.Thermal Properties of Poly[(disilanyene)oligophenylenes]" J.Organomet.Chem.564. 47-56 (1998)
[Publications] K.Wakita: "An Unexpected Elimination of Cyclopentadienide Anion in the Reaction of Silacyclohexadienes with a Bulky Aryllithium" Chem.Lett.687-688 (1998)
[Publications] H.Suzuki: "Synthesis,Structure,and Reactivity of the First Kinetically Stabilized Silanethione" J.Am.Chem.Soc.120. 11096-11105 (1998)
[Publications] S.Yamazaki-Nishida: "Theoretical study on the reactivity of phenyl cation with propyl group at ortho-position" J.Org.Chem.(印刷中).
[Publications] A.Sekiguchi: "The Chemistry of Organic Silicon Compounds.Vol.2,Chapter3" John Wiley & Sons, 34 (1998)
[Publications] H.Sakurai: "The Chemistry of Organic Silicon Compounds.Vol.2,Chapter15" John Wiley & Sons, 29 (1998)
[Publications] 永瀬茂: "「高周期典型元素化合物の特徴-理論的考察」,化学総説34(有機超原子価化合物)日本化学会編" 学会出版センター, 12 (1998)

1998 Fiscal Year Annual Research Report

比較元素論的14族元素低配位活性種の構造と反応性

Principal Investigator

吉良 満夫 東北大学, 大学院・理学研究科, 教授 (40004452)

Research Products

[Publications] T.Iwamoto: "Bimolecular reactions of tetrakis(trialkylsilyl)disilenes with various reagents" Bull.Chem.Soc.Jpn.71. 2741-2747 (1998)

[Publications] T.Iwamoto: "The First Stable Cyclotrisilene" J.Am.Chem.Soc.121(4). 886-887 (1999)

[Publications] H.Ogino: "Bridged silylene and germylene complexes" Adv.Organomet.Chem.42. 224-290 (1998)

[Publications] H.Tobita: "Synthesis and properties of intramolecularly base-stabilized disilany(silylene)ruthenium and-iron complexes" Organometallics. 17. 2850-2856 (1998)

[Publications] T.Veszpremi: "An ab initio MO study of structure and reactivity of 4-silatriafulvene" J.Am.Chem.Soc.120(10). 2408-2414 (1998)

[Publications] S.Tsutsui: "Bis(diisopropylamino)silylene and its dimer" J.Am.Chem.Soc.120(38). 9955-9956 (1998)

[Publications] M.Ichinohe: "Synthesis and Structure of Cyclotrigemenium Salt of the Tetrakis{3,5-bis(trifluoromethyl)phenyl}borate Anion,A Stable Free Germyl Cation in the Condensed Phase" Chem.Lett.1045-1046 (1998)

[Publications] S.Kyushin: "Highly Planar Silane[(i-Pr)3Si]3SiH and Silyl Radical[(i-Pr)3Si]3Si" Chem.Lett.2. 107-108 (1998)

[Publications] T.Yoshinaga: "Solid Surface Enhancement Effects on Chemiluminescence.II.Diaryloxalate and Polymers as Media Solids" J.Lumin.78. 221-229 (1998)

[Publications] M.Taguchi: "Chemical Tracks of Heavy Ions for 1,2,4,5-Tetracyanobenzen Anion Radical Formation" Nucl.Instrum.Meth.B. 134. 427-430 (1998)

[Publications] T.Sanji: "Highly Selective Mono-and Polyallylation of polychlorosilanes and Polyshlorodisilanes^1" Organometallics. 17(23). 5068-5071 (1998)

[Publications] D.Sasaki: "Optical characteristics of ultrathin oligosilane films prepared by molecular beam deposition method" Jpn.J.Appl.Phys.37. 953-955 (1998)

[Publications] K.Mochida: "Radical Anions of Oligogermanes,Me(Me2Ge)nMe(n=2,3,5,10)Generated by Pulse Radiolysis" Chem.Lett.2263-2264 (1998)

[Publications] K.Mochida: "Radical Cation of Dedecamethylcyclohexagermane Generated by Pulse Radiolysis" Chem.Lett.3-4 (1999)

[Publications] T.Akasaka: "Photochemical Bissilylation of C60 with Disilane" J.Org.Chem.64. 566-569 (1999)

[Publications] H.Yokoi: "In-Cage Formation of Carbanions in Photoinduced Electron-Transfer Reaction of Carboxylate Ions" J.Am,Chem.Soc.120. 12453-12458 (1998)

[Publications] H.Tomioka: "Persistent High-Spin Polycarbene.Generation of Polybrominated Tris-1,3,5-[4-(phenylcarbeno)-phenylethynyl]benzene(S=3)and Spin Identification by 2D Electron Spin Transient Nutation(2D-ESTN)Spectroscopy)" J.Am.Chem.Soc.120. 1106-1107 (1998)

[Publications] S.Murata: "Photochemistry of 2,4-Bis(diazo)-1,2,3,4-tetrahydronaphthalene-1,3-dione:Selective Photodecomposition of One of the Two Inequivatent Diazo Groups" J.Am.Chem.Soc.120. 9088-9089 (1998)

[Publications] Y.Yoshimi: "A Novel Photorearrangement of Aryl Naphthylemethyl Ethers.Formation of Cyclohexa-2,4-dienone Derivatives" Tetrahedron Lett.39. 4683-4686 (1998)

[Publications] K.Mizuno: "A Novel Intramolecular photocyclization of 2-(4,5-Dimethyl-2-oxa-4-hexenyl)-1-methoxycarbonylnaphthalene via 1,9-Hydrogen Abstraction" Chem.Commun.1659-1660 (1998)

[Publications] K.Tokunaga: "Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:Evaluation of π Conjugative Stabilization of α-Thiocarbonyl Carbocations" J.Org.Chem.63(7). 2209-2217 (1998)

[Publications] Y.Tanaka: "Self-Condensation Reaction of Lithium(Alkoxy)silylenoid:A Model Study by ab Initio Calculation" Organometallics. 17(21). 4573-4577 (1998)

[Publications] A.Kawachi: "Reaction of{Tris[2-(dimethylamino)phenyl]germyl}lithium with Elemental Selenium:Formation of 2,2,4,4-Tetrakis[2-(dimethylamino)phenyl]-1,3,2,4-diselenadigermetane" Chem.Lett.1. 21-22 (1999)

[Publications] A.Naka: "The reactions of tris(trimethylsiyl)silyllithium with ketenes" J.Organomet.Chem.(印刷中).

[Publications] A.Naka: "Synthesis and Platinum-and Palladium-Catalyzed Reactions of Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene)" Organometallics. 17(26). 5830-5835 (1998)

[Publications] J.Ohshita: "Synthesis and Properties of Dithienosiloles" J.Organomet.Chem.553. 487-491 (1998)

[Publications] J.Ohshita: "Polymeric Organosilicon Systems.XXIX.Thermal Properties of Poly[(disilanyene)oligophenylenes]" J.Organomet.Chem.564. 47-56 (1998)

[Publications] K.Wakita: "An Unexpected Elimination of Cyclopentadienide Anion in the Reaction of Silacyclohexadienes with a Bulky Aryllithium" Chem.Lett.687-688 (1998)

[Publications] H.Suzuki: "Synthesis,Structure,and Reactivity of the First Kinetically Stabilized Silanethione" J.Am.Chem.Soc.120. 11096-11105 (1998)

[Publications] S.Yamazaki-Nishida: "Theoretical study on the reactivity of phenyl cation with propyl group at ortho-position" J.Org.Chem.(印刷中).

[Publications] A.Sekiguchi: "The Chemistry of Organic Silicon Compounds.Vol.2,Chapter3" John Wiley & Sons, 34 (1998)

[Publications] H.Sakurai: "The Chemistry of Organic Silicon Compounds.Vol.2,Chapter15" John Wiley & Sons, 29 (1998)

[Publications] 永瀬 茂: "「高周期典型元素化合物の特徴-理論的考察」,化学総説34(有機超原子価化合物)日本化学会編" 学会出版センター, 12 (1998)

吉良満夫東北大学, 大学院・理学研究科, 教授 (40004452)

[Publications] 永瀬茂: "「高周期典型元素化合物の特徴-理論的考察」,化学総説34(有機超原子価化合物)日本化学会編" 学会出版センター, 12 (1998)