1994 年度実績報告書

無機金属化学

研究課題

研究課題/領域番号	06353004
研究機関	東北大学
研究代表者	荻野博東北大学, 理学部, 教授 (00004292)
研究分担者	田中晃二分子科学研究所, 教授 (00029274) 中沢浩分子科学研究所, 助教授 (00172297) 下井守東京大学, 教養学部, 助教授 (30092240) 吉田壽勝大阪府立大学, 総合科学部, 教授 (50029443) 巽和行名古屋大学, 理学部, 教授 (10155096)
キーワード	無機金属化学 / 無機金属化合物 / 配位化学 / Wemer型錯体 / 有機金属化学
研究概要	A Wemerが配位説を発表してから約100年が経過した。以来,いわゆるWemer型錯体の化学は,配位化学として無機化学の中で重要な位置を占めている。一方、19世紀前半に発見された金属一炭素結合を持つ化合物,すなわち有機金属化合物は時の経過と共にその例を増し,有機金属化学としてその体系をととのえた。しかしながら,従来の配位化学,有機金属化学のどれにも属さないがこれらと密接に関係する膨大な化合物群の化学がある。すなわち,金属と炭素を除く非金属元素との間に結合を持つ化合物の化学である。そこで,本研究者代表者は無機金属化学(Inorganometallic Chemistry)を提案し,均衡のとれた化学の展開を目指すべき時期が到来したと考えた。上の定義によれば,配位化合物も無機金属化合物に含まれてしまう。しかし,無機金属化学は配位化学が発展していたときには知られていなかった,あるいは思いも及ばなかった新しい型の結合様式や複雑な構成を持つ化合物の化学に力点を置くことにした。なぜなら,古典的なWemer型錯体ではなく,現代化学の中心的役割を担う化合物の化学として,無機金属化学を捉えたかったからである。本総合研究(B)は,現在考え得る最適任と言ってよい15名の研究者で組織した。各研究者によって取り上げられている化合物は極めて多彩で,金属とすべての族の非金属元素(13族〜17族元素)との間に結合を持つ化合物が含まれている。すなわち,非金属元素としては,13族(B),14族(Si,Ge),15族(O,S,Se),16族(N,P),17族(F,Cl)が含まれている。また,これら無機金属化合物と各種基質との間での物質変換反応や電子移動反応が取り上げられているほか,金属タンパク質やスーパーオキシドディスムターゼなどを無機金属化学の立場から研究したものもある。いずれも無機金属化学の将来の大きな発展を確信させるものである。

研究成果
(29件)

すべてその他

すべて文献書誌 (29件)

[文献書誌] Yasuro Kawano: "Synthesis and reactivity of the osmate(0) complexes M〔Os(CO)_2η-(C_5R_5)〕(M=Li,Na;R=H,Me):Versatile synthons for synthesis of organoosmium complexes." Organometallics. 13. 3849-3853 (1994)
[文献書誌] Toshiaki Mitsui: "Syntheses of colso-Cp'_2(CO)_3Fe_2MS_2 clusters(Cp'=η^5-C_5Me_5;M=Fe,Ru)and molecular structure of Cp_2(CO)_3Fe_3S_2" Inorg.Chem.33. 4934-4936 (1994)
[文献書誌] Yoshinori Naruta: "Oxygen evolution by water oxidation with manganase poyphyrin dimers." Angew.Chem.,Int.Ed.Engl.33. 1839-1842 (1994)
[文献書誌] Yoshinori Naruta: "Importance of Min-Mn separation and their relative arrangement on the development of high catalase activity in manganase porphyrin dimer" J.Chem.Soc.,Chem.Commun.1994. 2667-2668 (1994)
[文献書誌] Toshikatsu Yoshida: "Reversible addition of carbonyl compounds to parent imido complex:Preparation and crystal structure of trans-{Mo(NH)(OTf)(syn-Me_8[16]aneS_4)}OTf" J.Chem.Soc.,Chem.Commun.1994. 151-152 (1994)
[文献書誌] Hiroshi Nakazawa: "Formation and fac-mer isomerization of cationic phosphenium transition-metal complexes formulated as [M(bpy)(CO)_3{PN(Me)CH_2CH_2NMe}]^+(M=Cr,Mo,W)" J.Organomet.Chem.465. 193-198 (1994)
[文献書誌] Hiroshi Nakazawa: "Reactions of acyl(phosphonato)palladium complexes,Pd(PMe_3)_3{C(O)R'}{P(O)(OR)_2)},with an alkyl cation,yielding cationic phosphite complexes,and with acid chlorides." Organometallics. 33. 941-946 (1994)
[文献書誌] Isao Taniguchi: "Polypeptide-modified indium oxideelectrodes for direct electron transfer of ferredoxin." J.Chem.Soc.,Chem.Commun.1994. 953-954 (1994)
[文献書誌] F.M.Hawkridge: "The direct electron transfer reactions of cytochromec at electrode surfaces." Comments on Inorg.Chem.17. 163-187 (1995)
[文献書誌] Tetsuo Nagano: "Long-term administration of L-arginine improves nitric oxide release from kidney in DOCA salt hypertensive rats." Hypertension. 23. 752-756 (1994)
[文献書誌] Tetsuo Nagano: "Comparison of singlet oxygen production efficiency of C60 with other photosensitizers,based on 1268 nm emission." Chem.Pharm.Bull.42. 2291-2294 (1994)
[文献書誌] Nobumasa Kitajima: "A monomeric side-on peroxo manganese(III)complex:Mn(O_2)(3,5-iPr_2pzH)(HB(3,5-iPr_2pz)_3)." J.Am.Chem.Soc.116. 11596-11597 (1994)
[文献書誌] Nobumasa Kitajima: "Monomeric carboxylate ferrous complexes as models for the dioxygen binding sites in non-heme iron proteins.The reversible formation and characterization of μ-peroxo diferric complexes." J.Am.Chem.Soc.116. 9071-9082 (1994)
[文献書誌] Shunichi Fukuzumi: "Addition of organosilanes with aromatic carbonyl compounds via photoinduced electron transfer in the presence of magnesium perchlorate." J.Am.Chem.Soc.116. 5503-5504 (1994)
[文献書誌] K.M.Zaman: "Charge-transfer complexes acting as real intermediates in hydride transfer from Michler's hydride to 2,3-dichloro-5,6-dicyano-p-benzoquinone via electrontransfer." J.Am.Chem.Soc.116. 12099-12100 (1994)
[文献書誌] Takanori Nishioka: "Syntheses and crystal structures of triangular rhodium and iridium complexes with triply bridging sulfido ligands." Chem.Lett.1994. 1661-1664 (1994)
[文献書誌] Kiyoshi Isobe: "[{Rh_2Cp*_2(μ-CH_2)_2}_2(μ-S_4)]^<2+>:A novel tetranuclear cationic complex with a rectangular S_4 unit." Angew,Chem.Int.Ed.Engl.33. 1882-1883 (1994)
[文献書誌] Kazuhiko Mizuno: "Photochemical carbon-silicon bondforming reaction on electron-deficient alkenes by disilanes and polysilanes via photoinduced electron transfer." J.Organomet.Chem.473. 35-43 (1994)
[文献書誌] Kazuyuki Tatsumi: "A zigzag chain structure of a 3-thiapentane-1,5-dithiolato vanadium complex linked by lithium ions." J.Chem.Soc.,Chem.Commun.1995. 111-112 (1995)
[文献書誌] Kazuyuki Tatsumi: "Linear vs bent M-O-R bonds in d^0 metal alkoxides:X-ray crystal structure of (C_5Me_5)Ta(S^tBu)_3(O^nBu)_3 and EHMO analysis." J.Organomet.Chem.471. 111-115 (1994)
[文献書誌] Takashi Shibahara: "^<31>PNMR studies on sulfur/oxygen-bridged incomplete cubane-type molybdenum cluster compounds." Inorg.Chem.34. 42-48 (1995)
[文献書誌] Takashi Shibahara: "Sulfur-bridged couble cubane-type tungsten-nickel mixed-metal cluster.Synthesis and X-ray structure of[{W_3NiS_4(H_2O)_9O}_2(CH_3C_6H_4SO_3)_8)・20H_2O." Chem.Lett.1231-1234. 1994 (1994)
[文献書誌] Yoshinori Kushi: "Oxalate formation in electrochemical CO_2 reduction catalyzed by rhodium-sulfur cluster." Chem.Lett.1994. 2175-2178 (1994)
[文献書誌] Hirotaka Nagao: "Carbon-carbon bond formation in the electrochemical reduction of carbon dioxide catalyzed by a ruthenium complex." Inorg.Chem.33. 3415-3420 (1994)
[文献書誌] 成田吉徳: "現代錯体化学" 講談社サイエンティフィク、基礎錯体工学研究会編, 220 (1994)
[文献書誌] Yoshinori Naruta: "Metalloporphyrines in catalytic oxidations" Marcel Dekker, 390 (1994)
[文献書誌] Kazuhiko Mizuno: "Photochemical key steps in organic synthesis" VCH Publishers, 350 (1994)
[文献書誌] Kazuhiko Mizuno: "Topics in Current Chemistry,Vol.169,Electron Transfer I" Springer-Verlag, 371 (1994)
[文献書誌] 谷口功: "二酸化炭素-化学、生化学、環境" 東京化学同人, 192 (1994)

1994 年度 実績報告書

無機金属化学

研究代表者

荻野 博 東北大学, 理学部, 教授 (00004292)

研究成果

[文献書誌] Yasuro Kawano: "Synthesis and reactivity of the osmate(0) complexes M〔Os(CO)_2η-(C_5R_5)〕(M=Li,Na;R=H,Me):Versatile synthons for synthesis of organoosmium complexes." Organometallics. 13. 3849-3853 (1994)

[文献書誌] Toshiaki Mitsui: "Syntheses of colso-Cp'_2(CO)_3Fe_2MS_2 clusters(Cp'=η^5-C_5Me_5;M=Fe,Ru)and molecular structure of Cp_2(CO)_3Fe_3S_2" Inorg.Chem.33. 4934-4936 (1994)

[文献書誌] Yoshinori Naruta: "Oxygen evolution by water oxidation with manganase poyphyrin dimers." Angew.Chem.,Int.Ed.Engl.33. 1839-1842 (1994)

[文献書誌] Yoshinori Naruta: "Importance of Min-Mn separation and their relative arrangement on the development of high catalase activity in manganase porphyrin dimer" J.Chem.Soc.,Chem.Commun.1994. 2667-2668 (1994)

[文献書誌] Toshikatsu Yoshida: "Reversible addition of carbonyl compounds to parent imido complex:Preparation and crystal structure of trans-{Mo(NH)(OTf)(syn-Me_8[16]aneS_4)}OTf" J.Chem.Soc.,Chem.Commun.1994. 151-152 (1994)

[文献書誌] Hiroshi Nakazawa: "Formation and fac-mer isomerization of cationic phosphenium transition-metal complexes formulated as [M(bpy)(CO)_3{PN(Me)CH_2CH_2NMe}]^+(M=Cr,Mo,W)" J.Organomet.Chem.465. 193-198 (1994)

[文献書誌] Hiroshi Nakazawa: "Reactions of acyl(phosphonato)palladium complexes,Pd(PMe_3)_3{C(O)R'}{P(O)(OR)_2)},with an alkyl cation,yielding cationic phosphite complexes,and with acid chlorides." Organometallics. 33. 941-946 (1994)

[文献書誌] Isao Taniguchi: "Polypeptide-modified indium oxideelectrodes for direct electron transfer of ferredoxin." J.Chem.Soc.,Chem.Commun.1994. 953-954 (1994)

[文献書誌] F.M.Hawkridge: "The direct electron transfer reactions of cytochromec at electrode surfaces." Comments on Inorg.Chem.17. 163-187 (1995)

[文献書誌] Tetsuo Nagano: "Long-term administration of L-arginine improves nitric oxide release from kidney in DOCA salt hypertensive rats." Hypertension. 23. 752-756 (1994)

[文献書誌] Tetsuo Nagano: "Comparison of singlet oxygen production efficiency of C60 with other photosensitizers,based on 1268 nm emission." Chem.Pharm.Bull.42. 2291-2294 (1994)

[文献書誌] Nobumasa Kitajima: "A monomeric side-on peroxo manganese(III)complex:Mn(O_2)(3,5-iPr_2pzH)(HB(3,5-iPr_2pz)_3)." J.Am.Chem.Soc.116. 11596-11597 (1994)

[文献書誌] Nobumasa Kitajima: "Monomeric carboxylate ferrous complexes as models for the dioxygen binding sites in non-heme iron proteins.The reversible formation and characterization of μ-peroxo diferric complexes." J.Am.Chem.Soc.116. 9071-9082 (1994)

[文献書誌] Shunichi Fukuzumi: "Addition of organosilanes with aromatic carbonyl compounds via photoinduced electron transfer in the presence of magnesium perchlorate." J.Am.Chem.Soc.116. 5503-5504 (1994)

[文献書誌] K.M.Zaman: "Charge-transfer complexes acting as real intermediates in hydride transfer from Michler's hydride to 2,3-dichloro-5,6-dicyano-p-benzoquinone via electrontransfer." J.Am.Chem.Soc.116. 12099-12100 (1994)

[文献書誌] Takanori Nishioka: "Syntheses and crystal structures of triangular rhodium and iridium complexes with triply bridging sulfido ligands." Chem.Lett.1994. 1661-1664 (1994)

[文献書誌] Kiyoshi Isobe: "[{Rh_2Cp*_2(μ-CH_2)_2}_2(μ-S_4)]^<2+>:A novel tetranuclear cationic complex with a rectangular S_4 unit." Angew,Chem.Int.Ed.Engl.33. 1882-1883 (1994)

[文献書誌] Kazuhiko Mizuno: "Photochemical carbon-silicon bondforming reaction on electron-deficient alkenes by disilanes and polysilanes via photoinduced electron transfer." J.Organomet.Chem.473. 35-43 (1994)

[文献書誌] Kazuyuki Tatsumi: "A zigzag chain structure of a 3-thiapentane-1,5-dithiolato vanadium complex linked by lithium ions." J.Chem.Soc.,Chem.Commun.1995. 111-112 (1995)

[文献書誌] Kazuyuki Tatsumi: "Linear vs bent M-O-R bonds in d^0 metal alkoxides:X-ray crystal structure of (C_5Me_5)Ta(S^tBu)_3(O^nBu)_3 and EHMO analysis." J.Organomet.Chem.471. 111-115 (1994)

[文献書誌] Takashi Shibahara: "^<31>PNMR studies on sulfur/oxygen-bridged incomplete cubane-type molybdenum cluster compounds." Inorg.Chem.34. 42-48 (1995)

[文献書誌] Takashi Shibahara: "Sulfur-bridged couble cubane-type tungsten-nickel mixed-metal cluster.Synthesis and X-ray structure of[{W_3NiS_4(H_2O)_9O}_2(CH_3C_6H_4SO_3)_8)・20H_2O." Chem.Lett.1231-1234. 1994 (1994)

[文献書誌] Yoshinori Kushi: "Oxalate formation in electrochemical CO_2 reduction catalyzed by rhodium-sulfur cluster." Chem.Lett.1994. 2175-2178 (1994)

[文献書誌] Hirotaka Nagao: "Carbon-carbon bond formation in the electrochemical reduction of carbon dioxide catalyzed by a ruthenium complex." Inorg.Chem.33. 3415-3420 (1994)

[文献書誌] 成田吉徳: "現代錯体化学" 講談社サイエンティフィク、基礎錯体工学研究会編, 220 (1994)

[文献書誌] Yoshinori Naruta: "Metalloporphyrines in catalytic oxidations" Marcel Dekker, 390 (1994)

[文献書誌] Kazuhiko Mizuno: "Photochemical key steps in organic synthesis" VCH Publishers, 350 (1994)

[文献書誌] Kazuhiko Mizuno: "Topics in Current Chemistry,Vol.169,Electron Transfer I" Springer-Verlag, 371 (1994)

[文献書誌] 谷口 功: "二酸化炭素-化学、生化学、環境" 東京化学同人, 192 (1994)

1994 年度実績報告書

荻野博東北大学, 理学部, 教授 (00004292)

[文献書誌] 谷口功: "二酸化炭素-化学、生化学、環境" 東京化学同人, 192 (1994)