1994 Fiscal Year Annual Research Report

金属錯体における立体化学の新しい展開

Research Project

Project/Area Number	06303004
Research Institution	Okazaki National Research Institutes
Principal Investigator	吉川雄三岡崎国立共同研究機構, 分子科学研究所, 教授 (30022643)
Co-Investigator(Kenkyū-buntansha)	中村晃分子科学研究所, 教授 (80029404) 安井隆次高知大学, 理学部, 教授 (20028161) 宇津野峻司静岡大学, 理学部, 教授 (40021935) 福田豊お茶の水女子大学, 理学部, 教授 (30021950) 海崎純男大阪大学, 理学部, 教授 (20089874)
Keywords	金属錯体 / 立体化学 / 機能性 / 立体規制 / 酵素モデル
Research Abstract	本年度は初年度ではあるが、各研究分担者は、研究課題に込められた意図をよく理解し、わが国における今後の錯体化学の進べき方向を模索する意味も含めて、意欲的にとり組み、分担課題を進展させている。それらの途中経過は昨年12月14、15日に開催したシンポジウムで発表され、全体で討議された。字数の制約があるので今年度各自が発展させた研究を分担者名と共に以下に列挙する。「プロペラ型金属錯体の示す誘起円二色性スペクトル」(宇津野峻司)、「アルコール溶媒中でのfac-[Cr(leu)_3]の立体選択性について」(沖久也)、「複数のキラル中心を有する金属化合物の立体化学的研究」(岡本健一)、「金属錯体における分子間水素結合による立体制御」(海崎純男)、「新規なフタロシアニン金属錯体の合成と特性」(春日邦宣)、「光学活性硫黄架橋のクラスター錯体」(柴原隆志)、「不斉リン原子を含む多座配位子とその金属錯体の合成」(柏原和夫)、「異節縮合環をキレート環とする遷移金属錯体の合成と反応性」(後藤正文)、「金属錯体ジアステレオマ-における不斉識別の機構」(久司佳彦)、「直線状に立体制御された金属クラスターの合成」(中村晃)、「軸性キラリティーを有するコバルト(III)錯体」(仲野義晴)、「金属錯体の酸素分子活性化の機能」(西田雄三)、「光照射によるコバルト(III)錯体の連結異性化および幾何異性化」(小島正明)、「キラルな含硫錯体の光異性化と多核化反応について」(安井隆次)、「高歪亜鉛錯体の配位立体化学と反応性」(藤井有起)、「金属-金属結合切断を伴う遷移金属錯体の転移反応」(中沢浩)、「[CpFe(CO)(PPh_3)L]錯体の構造とA-[Ru(phen)_3]Cl_2による識別の選択性」(三吉克彦)、「複核錯体の配位立体構造制御とサーモクロミズム」(福田豊)。これらの詳細は、掲載した研究発表の表および各論文内容により知ることができる。

Research Products

(31 results)

All Other

All Publications (31 results)

[Publications] M.Kojima: "Photochemistry of Tris(L-cysteinesultinato-N.S)cobaltate(III).Linkage Isomenzation from Sultinato-S to Sultinato-O" Proc.Japan Acad.70B. 101-105 (1994)
[Publications] M.Goto: "Dependence of Dehydrogenation of Amines towards Coordination Geometry - Oxidation-Products of Tricyano[Di(2-Pyridylmethyl)Amine]Ferrate from mer and fac Isomers" J.Chem.Soc.Chem.Commun. 2015-2016 (1994)
[Publications] H.Kurosaki: "Preparation and NMR-Spectra of Hexacoordinate Metal Complexes of Mono(N-ethylethanediamine)and Mono(N-benzlylethanediamine) and Crystal-structure of [CO(NH_3)_4(N-benzylethanediamine)](NO_3)_3・-1.5H_2O" Bull.Chem.Soc.Jpn.68. (1995)
[Publications] H.Nakazawa: "Reactions of Acyl(phosphonato)palladium Complexes,Pd(PMe_3)_2{C(O)R}-{P(C)(OR)_2}, with an Alkyl Cotion, Yieding Cationic Phosphite Complexes and with Acid-chlorides, Involving Facile Pd-P(O)(OR)_2 Bond-Cleavege" Organomatallics. 13. 941-946 (1994)
[Publications] H.Nakazawa: "Conversicn of Cationic Phosphite Complexes into Phosphonate Complexes with Selective Deamination in the Coordinating Phosphorus - reaction of [(η^5-C_5H_5)L_2Fe{P(NC_4H_8)_n(Omo)_<3-n>)]^+(L=CO,Pme_3) with KOH to Afford (η^5-(C_5H_5)L_2Fe{P(O)(NC_4H_8)_<n-1>(OMo)_<3-n>}" Inorg.Chim.Acta.222. 123-129 (1994)
[Publications] T.Mizuta: "Highly Efficient Chromatographic Optical Resolution of Fac-Tris(β-alaninato)cobalt(III)with an Optically-Active ob_3 Isomer of Tris(trans-1,2-diaminocyclohexane)cobalt(III) cation Adsorbed on a Cation-Excharge Resin" Chem.Lett.101-104 (1994)
[Publications] H.Yoneda: "mechanism of Potical Resolution of Octahedral Complexes" ACS Sympoium Series. 565. 308-317 (1994)
[Publications] J.Fujita: "Crystal Structures of Cobalt(III)Complexes Containing 1,1,1,-tris(dimothylphesphonomethyl)-ethane(mmtp).[CoCi_2(mmtp)] and [Co(Cr^1)_38mmtp)]・2H_2O." Bull.Chem.Soc.Jpn.67. 2145-2150 (1994)
[Publications] S.Ohba: "Crystal Structures of trans-[CoCl_2{(CH_3)_2PCH_2CH_2P(CH_3)_2}_2] ClO_4,trans(Cl,Cl)cis(P,P)-[CoCl_2{NH_2CH_2CH_2-P(OH_3)_2}] _2PF_6・0.5CH_3OH,and trans[CoCl_2(NH_2CH_2CH_2NH_2)_2] NO_3" Bull.Chem.Soc.Jpn.67. 2457-2462 (1994)
[Publications] N.Shintani: "Studies on Mised Chelatis.XXXII.Five Coordinate Copper(II)Chelates with N,N,N',N''-Pentamethyldiethylenetriamine and β-Diketonates" Bull.Chem.Soc.Jpn.67. 1828-1834 (1994)
[Publications] Y.Nakao: "Synthesis and Properties of Dinuclear Copper(II)Complexes Containing Dinucleating Ligands with Imudazole Nitrogen and Two Exegeroas Bridging Ligands." Bull.Chem.Soc.Jpn.67. 2586-2589 (1994)
[Publications] T.Yasui: "Stereoselective isomerization of chiral Cobalt(III) Complexes" Polyhedron. 13(13). 1963-1968 (1994)
[Publications] T.Yonemura: "Stereospecific Deuteration of Chelated 2,2'-Thiodiacetati(tda)in [Co(dien)(tda)]^+(dien=diethylenetriamine).Observed in the Acidic D_2O Solations" Chemistry Letters. 59-60 (1995)
[Publications] N.Sakagami: "Crystal Soructure of the(Ethylenediamine-N,N'-dipropionato)-(ethylenediamine)cobalt(III) Isomers." Bull.Chem.Soc.Jpn.67. 630-686 (1994)
[Publications] S.Kaizaki: "Structural Characterization of Octahedral Metal Complexes of [MX_3(py)_3] Type with Three Pyridines as Revealed by ^2HNMR Spectra" Inorg.Chim.Acta.218. 179-184 (1994)
[Publications] Y.Yao: "^<31>PNMR Studies on Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum Cluster Compounds. X-ray Structures of [Mo_3OS_3(DTP)_4(CH_3CN)] and [Mo_3OS_3(OAc)(DTP)_2(Py)_2(OC_2H_5)]" Inorg.Chem.34. 42-48 (1995)
[Publications] T.Shibahara: "Sulfur-Bridged Double Cubane-Type Tungsten-Nickel Mixed-Metal Cluster. Synthesis and X-Ray Structure of [{W_3NiS_4(H_2O)_9}_2](CH_3C_6H_4SO_3)_8・20H_2O" Chem.Lett. 1231-1234 (1994)
[Publications] K.Sato: "Stereospecific Biading of Chemically Modified Salen-type Schiff Bose Complexes of Copper(II)with DNA" J.Chem.Soc.,Chem.Commun.625-626 (1994)
[Publications] M.Sato: "Structure Analyses of Nickel(II)Conplexes Bound to Copolymers of 2-Acetyl-5-(4-vinylbenzyloxy)phenol,Acrylamide,and 2,2'-Methylenediacrylamide by EXAFS and XANES" Bull.Chem.Soc.Jpn.67. 1954-1956 (1994)
[Publications] K.Kanamori: "Relationship between OXo-Bridoed Diner Formation and Structure of Vonadium(III) Amino Polycar boxylates." Inorg.Chem.33. 5547-5554 (1994)
[Publications] T.Konno: "Synthesis and Properties of Linear-Type S-Bridged Rh^<III>Ni^<II>Rh^<III> Trinuclear Complexes with 2-Aminoethanethiolate (aet) or L-cysteinate (L-cys).Crystal Stracture of [Ni{Rh(aet)_3}_2](NO_3)_2" Bull.Chem.Soc.Jpn.68. 610-615 (1995)
[Publications] Y.Nishida: "On the chemical mechanism of aldehyde metabolism by cytochrome P-450" Polyhedron.13. 2473-2476 (1994)
[Publications] Y.Nishida: "Chemical mechanism of dioxygen activation by trans-[FeCl_2(cyclam)]^T in the presence of redacing agents sach as aliphetic alolehyde or Linolenic acid." J.Chem.Soc.,Dalton Trans.2805-2808 (1994)
[Publications] K.Mashima: "Diene Complexes of Calciam and Strontium - First Crystal - Structures of Calciam-Diene and Strontium-Diene Complexes.M(2,3-dimethyl-1,4-diphenyl-1,3-butadiene)(THF)_4(M=Ca and Sr)" J.Am.Chem.Soc.116. 6977-6978 (1994)
[Publications] K.Mashima: "Formation of Lanthanoid (II) and Lanthanoid(III) Thiolate Complexes derived from Metals and Organic Disulfides:Crystal-Structures of [(Ln(SAr)(Mu-SAr)(Thf)_3)_2](LN=SM,EU).[SM(SAr)_3(Py)_22(Thf)] and [Yb(SAr)_3(Py)_3] Ar=2,4,6-Triisopropylphenyl Py=Pyridine" J.Chem.Soc.Chem.Commun. 2523-2524 (1994)
[Publications] H.Oki: "Stereoselective Preparation and Characterization of [Cr(amino acidato)_2(amino-acidato-N)(Me_2SO)]Complexes" Bull.Chem.Soc.Jpn.67. 1825-1827 (1994)
[Publications] R.Nakata: "Ligurd chromatography of Diastereoisomers on neutral tris-and bis-(L-α-aminoacidato)chromium(III) complexes" Analytical Sciences. 10. 663-665 (1994)
[Publications] M.Hirotsu: "Streic Control of Redor Potentials of cobalt(II) Schiff Base Conplexes with Phenyl Substituents" Chem.Lett.2392-2396 (1994)
[Publications] F.M.Akhter: "Photochemical Rection of(L-cysteinesulfinato-N,S){tris(2-aminoethyl)amine}cobalt(III).Formation of a Cobalt(III)Complex with an Uncoordinated Sulfinate Group" Chem.Lett.2393-2396 (1994)
[Publications] K.Kasuga: "Fluorescence spectra and wloration of a curopium(III)hexaaza macrocyclic complex in various solvents" Polyhedron. 13. 159-161 (1994)
[Publications] M.Handa: "Spectral and electrochemical properties of radical hexadecafluoro-phthalocyanine." Inorg.Chim.Acta. 230. 41-44 (1995)

1994 Fiscal Year Annual Research Report

金属錯体における立体化学の新しい展開

Principal Investigator

吉川 雄三 岡崎国立共同研究機構, 分子科学研究所, 教授 (30022643)

Research Products

[Publications] M.Kojima: "Photochemistry of Tris(L-cysteinesultinato-N.S)cobaltate(III).Linkage Isomenzation from Sultinato-S to Sultinato-O" Proc.Japan Acad.70B. 101-105 (1994)

[Publications] M.Goto: "Dependence of Dehydrogenation of Amines towards Coordination Geometry - Oxidation-Products of Tricyano[Di(2-Pyridylmethyl)Amine]Ferrate from mer and fac Isomers" J.Chem.Soc.Chem.Commun. 2015-2016 (1994)

[Publications] H.Kurosaki: "Preparation and NMR-Spectra of Hexacoordinate Metal Complexes of Mono(N-ethylethanediamine)and Mono(N-benzlylethanediamine) and Crystal-structure of [CO(NH_3)_4(N-benzylethanediamine)](NO_3)_3・-1.5H_2O" Bull.Chem.Soc.Jpn.68. (1995)

[Publications] H.Nakazawa: "Reactions of Acyl(phosphonato)palladium Complexes,Pd(PMe_3)_2{C(O)R}-{P(C)(OR)_2}, with an Alkyl Cotion, Yieding Cationic Phosphite Complexes and with Acid-chlorides, Involving Facile Pd-P(O)(OR)_2 Bond-Cleavege" Organomatallics. 13. 941-946 (1994)

[Publications] T.Mizuta: "Highly Efficient Chromatographic Optical Resolution of Fac-Tris(β-alaninato)cobalt(III)with an Optically-Active ob_3 Isomer of Tris(trans-1,2-diaminocyclohexane)cobalt(III) cation Adsorbed on a Cation-Excharge Resin" Chem.Lett.101-104 (1994)

[Publications] H.Yoneda: "mechanism of Potical Resolution of Octahedral Complexes" ACS Sympoium Series. 565. 308-317 (1994)

[Publications] J.Fujita: "Crystal Structures of Cobalt(III)Complexes Containing 1,1,1,-tris(dimothylphesphonomethyl)-ethane(mmtp).[CoCi_2(mmtp)] and [Co(Cr^1)_38mmtp)]・2H_2O." Bull.Chem.Soc.Jpn.67. 2145-2150 (1994)

[Publications] S.Ohba: "Crystal Structures of trans-[CoCl_2{(CH_3)_2PCH_2CH_2P(CH_3)_2}_2] ClO_4,trans(Cl,Cl)cis(P,P)-[CoCl_2{NH_2CH_2CH_2-P(OH_3)_2}] _2PF_6・0.5CH_3OH,and trans[CoCl_2(NH_2CH_2CH_2NH_2)_2] NO_3" Bull.Chem.Soc.Jpn.67. 2457-2462 (1994)

[Publications] N.Shintani: "Studies on Mised Chelatis.XXXII.Five Coordinate Copper(II)Chelates with N,N,N',N''-Pentamethyldiethylenetriamine and β-Diketonates" Bull.Chem.Soc.Jpn.67. 1828-1834 (1994)

[Publications] Y.Nakao: "Synthesis and Properties of Dinuclear Copper(II)Complexes Containing Dinucleating Ligands with Imudazole Nitrogen and Two Exegeroas Bridging Ligands." Bull.Chem.Soc.Jpn.67. 2586-2589 (1994)

[Publications] T.Yasui: "Stereoselective isomerization of chiral Cobalt(III) Complexes" Polyhedron. 13(13). 1963-1968 (1994)

[Publications] T.Yonemura: "Stereospecific Deuteration of Chelated 2,2'-Thiodiacetati(tda)in [Co(dien)(tda)]^+(dien=diethylenetriamine).Observed in the Acidic D_2O Solations" Chemistry Letters. 59-60 (1995)

[Publications] N.Sakagami: "Crystal Soructure of the(Ethylenediamine-N,N'-dipropionato)-(ethylenediamine)cobalt(III) Isomers." Bull.Chem.Soc.Jpn.67. 630-686 (1994)

[Publications] S.Kaizaki: "Structural Characterization of Octahedral Metal Complexes of [MX_3(py)_3] Type with Three Pyridines as Revealed by ^2HNMR Spectra" Inorg.Chim.Acta.218. 179-184 (1994)

[Publications] Y.Yao: "^<31>PNMR Studies on Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum Cluster Compounds. X-ray Structures of [Mo_3OS_3(DTP)_4(CH_3CN)] and [Mo_3OS_3(OAc)(DTP)_2(Py)_2(OC_2H_5)]" Inorg.Chem.34. 42-48 (1995)

[Publications] T.Shibahara: "Sulfur-Bridged Double Cubane-Type Tungsten-Nickel Mixed-Metal Cluster. Synthesis and X-Ray Structure of [{W_3NiS_4(H_2O)_9}_2](CH_3C_6H_4SO_3)_8・20H_2O" Chem.Lett. 1231-1234 (1994)

[Publications] K.Sato: "Stereospecific Biading of Chemically Modified Salen-type Schiff Bose Complexes of Copper(II)with DNA" J.Chem.Soc.,Chem.Commun.625-626 (1994)

[Publications] M.Sato: "Structure Analyses of Nickel(II)Conplexes Bound to Copolymers of 2-Acetyl-5-(4-vinylbenzyloxy)phenol,Acrylamide,and 2,2'-Methylenediacrylamide by EXAFS and XANES" Bull.Chem.Soc.Jpn.67. 1954-1956 (1994)

[Publications] K.Kanamori: "Relationship between OXo-Bridoed Diner Formation and Structure of Vonadium(III) Amino Polycar boxylates." Inorg.Chem.33. 5547-5554 (1994)

[Publications] T.Konno: "Synthesis and Properties of Linear-Type S-Bridged Rh^<III>Ni^<II>Rh^<III> Trinuclear Complexes with 2-Aminoethanethiolate (aet) or L-cysteinate (L-cys).Crystal Stracture of [Ni{Rh(aet)_3}_2](NO_3)_2" Bull.Chem.Soc.Jpn.68. 610-615 (1995)

[Publications] Y.Nishida: "On the chemical mechanism of aldehyde metabolism by cytochrome P-450" Polyhedron.13. 2473-2476 (1994)

[Publications] Y.Nishida: "Chemical mechanism of dioxygen activation by trans-[FeCl_2(cyclam)]^T in the presence of redacing agents sach as aliphetic alolehyde or Linolenic acid." J.Chem.Soc.,Dalton Trans.2805-2808 (1994)

[Publications] K.Mashima: "Diene Complexes of Calciam and Strontium - First Crystal - Structures of Calciam-Diene and Strontium-Diene Complexes.M(2,3-dimethyl-1,4-diphenyl-1,3-butadiene)(THF)_4(M=Ca and Sr)" J.Am.Chem.Soc.116. 6977-6978 (1994)

[Publications] H.Oki: "Stereoselective Preparation and Characterization of [Cr(amino acidato)_2(amino-acidato-N)(Me_2SO)]Complexes" Bull.Chem.Soc.Jpn.67. 1825-1827 (1994)

[Publications] R.Nakata: "Ligurd chromatography of Diastereoisomers on neutral tris-and bis-(L-α-aminoacidato)chromium(III) complexes" Analytical Sciences. 10. 663-665 (1994)

[Publications] M.Hirotsu: "Streic Control of Redor Potentials of cobalt(II) Schiff Base Conplexes with Phenyl Substituents" Chem.Lett.2392-2396 (1994)

[Publications] F.M.Akhter: "Photochemical Rection of(L-cysteinesulfinato-N,S){tris(2-aminoethyl)amine}cobalt(III).Formation of a Cobalt(III)Complex with an Uncoordinated Sulfinate Group" Chem.Lett.2393-2396 (1994)

[Publications] K.Kasuga: "Fluorescence spectra and wloration of a curopium(III)hexaaza macrocyclic complex in various solvents" Polyhedron. 13. 159-161 (1994)

[Publications] M.Handa: "Spectral and electrochemical properties of radical hexadecafluoro-phthalocyanine." Inorg.Chim.Acta. 230. 41-44 (1995)

吉川雄三岡崎国立共同研究機構, 分子科学研究所, 教授 (30022643)