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1990 Fiscal Year Final Research Report Summary

Intramolecular Non-covalent Interactions in Metal Complexes : Geometrical Controles and Stereoselective Reactions

Research Project

Project/Area Number 62430011
Research Category

Grant-in-Aid for General Scientific Research (A)

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionKyushu University

Principal Investigator

OKAWA Hisashi  Kyushu Univ., Fac. of Sci., Assot. Prof., 理学部, 助教授 (00037219)

Co-Investigator(Kenkyū-buntansha) SHINMYOZU Teruo  Kyushu Univ., Fac. of Sci., Assot. Prof., 理学部, 助教授 (90037292)
KATSUKI Tsutomu  Kyushu Univ. Fac. of Sci., Professor, 理学部, 教授 (40037271)
MATSUMOTO Naohide  Kyushu Univ., Fac. of Sci., Assistant, 理学部, 助手 (80145284)
Project Period (FY) 1987 – 1990
KeywordsStereoselectivity / Non-covalent Interraction / X-Ray Crystal Structure / Circular dichroism / Enantioselectivity / Tetrahedral Complexes / Schiff Base Ligands
Research Abstract

Stereoselectivities of six-coordinate complexes of 4- (l-menthyloxy) -1-phenyl-1, 3-butanedione (H (l-moba) ) and 4- (l-menthyloxy) -1-p-tolly-1, 3-butanedione (H (l-moba-Me) ) have been examined for various metal ions (Co, Cr, Mn, IIIA, IIIB, Ianthanoid). In particular the complexes of IIIA and IIIB ions were studied by means of 400 MHz H-NMR and CD spectroscopies. All the complexes showed a stereoselectivity to afford the fac-OMEGA from predominantly because of the operation of a non-covalent interaction in the from of a left-handed three-bladed propeller, comprising three interligand l-menthyl/aryl contact. The interligand contact became efficient when the central metal ion was significantly large (r>l.OA^^゚).
Such sterically controlled lanthanoid complexes Ln (l-moba-Me)_3 were used as Lewis acid catalysts for enantioselective reductions of ketones. Acetophenone was converted into (S) -alcohol (e e % 84) whereas butane-2-one and octane-2-one were converted into (R) -alchols.
Stereose … More lectivities of tetrahedral or pseudo-tetrahedral Co (II), Cu- (II), and Zn (II) complexes of N- (l-menthyl) salicylaldimine (H (sal-ment) ) and N- (R) -alpha-methylbenzylsalicylaldimine (H (sal-Rmb) ) have been studied by single-crystal X-ray method, CD spectroscopy, and molecular mechnics Calculations. The preferred configuration was DELTA for tetrahedral [M (sal-ment)_2] (M=Co, Cu, Zn), OMEGA for tetrahedral [M (sal-Rmb)_2] (M=Co, Zn), and DELTA for pseudo-tetrahedral [Cu (sal-Rmb)_2]. The X-ray structural analyses for [M (sal-Rmb)_2] clearly demonstrated the operation of non-covalent interactions between the chiral N-substituent and the adjacent ring. The Cotton effect induced at the azomethine pi-pi^* transition was well correlated with the absolute configration about the metal center.
Stereoselectivities of planar metal (II) complexes (M=Cu, Pb, Pt)) of N-substituted ethylenediamines, N- { (R) -alpha-methylbenzyl} ethylenediamine (R-mben), N- { (S) -alpha-methylbenzyl} ethylenediamine (S-mben), and N- (l-menthyl) -ethylenediamine (mten), have been examined by electronic absorption and CD spectroscopies and interpreted based on a regional rule (hexadecadalrule). The preferred conformation with respect to the ethylene chain were delta for the mten and B-mben complexes and lambda for the S-mben complexes. Less

  • Research Products

    (48 results)

All Other

All Publications (48 results)

  • [Publications] Shuichi Maeda: "Noncovalent Interactions in Metal Complexes.XI.Synthesis and Stereoselectivity of 1:3 Cobalt(III) Complexes of 1ーlーMenthyloxyー3ー acetylacetone" Polyhedron,. 6. 583-586 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Michio Nakamura: "Noncovalent Interactions in Metal Complexes.14.Proton NMR Spectroscopic Investigation on Stereoselecーtivity in Co(III) Complexes of Various 3ーSubstituted 1ーPhenylー1,3ーpropanedione" Bull.Chem.Soc.Jpn.,. 60. 539-543 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hisashi Okawa: "Noncovalent Interactions in Metal Complexes.15.Stereoselectivity of Cobalt(III)Mixed Chelates with Bis (1ーlーmenthyloxyー3ーbenzoylacetone)ethylenediamine and a Diamine" Inorg.Chim.Acta,. 128. 155-159 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kaoru Horiuchi: "Cobalt(III) Complexes of Salen Analog with Thioether Pendant Group.XーRay Structure Analysis and Thioether Coordination Effect" Bull.Chem.Soc.Jpn.,. 60. 3575-3580 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masatomi Sakamoto: "Copper(II)ーLanthanoid(III) Complexes of Binucleating Ligands Derived from 3ーFormylsalicylic Acid and Diamines" Bull.Chem.Soc.Jpn.,. 61. 1613-1618 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masatomi Sakamoto: "Specific Binding of Substrates Containing Nitrogen and Oxygen Donor Groups to Copper(II)ーGadolinium(III) Heteroーmetal Center" Bull.Chem.Soc.Jpn.,. 61. 3319-3320 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hisashi Okawa: "Noncovalent Interactions in Metal Complexes" Coord.Chem.Rev.,. 92. 1-28 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hisashi Okawa: "Noncovalent Interactionsin Metal Complexes.18.Stereoselectivity of 1:3 Complexes of Sc,Y,La,Al,Ga,In Ions with 4ー(lーMenthyloxy)ー1ーphenylー1,3ーbutanedione and 4ー(lーMenthyloxy)ー1ーpーtolylー1,3ーbutanedione" Inorg,Chem.,. 27. 4373-4377 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Munetoshi Tomita: "Metal Complexes (CoAA3+BB,FeAA3+BB,MnAA3+BB)of the Quinquedentate Salen Analog,2ーMethylー4ーbenzylthioーN.N′ーbutaneー1,2ーdiylbis(salicylideneimine):Crystal Structure and Sulphur Coordination Effect" J.Chem,Soc.,Dalton Trans.,. 179-184 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kaoru Horiuchi: "Cobalt(II) and μーOxodiiron(III,IV)Complexes of Salen Analog with Aromatic Thioether Pendant Group,N,N′ーDisalicylideneー2ーmethylー4ー(2ーmethylthiophenyl)ー1,2ーbutanediamine" Inorg.Chim.Acta,. 144. 99-103 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naohide Matsumoto: "Synthesis and XーRay Crystal Structures of an Imidazolateーbridged Polynuclear Copper(II) Complex Exhibiting a Unique Helicoid Structure" J.Chem.Soc.,Dalton Trans.,. 1943-1948 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hisashi Okawa: "Enantioselective Reduction of Ketones on Stericallyーcontrolled Lanthanoid(III) Complexes" J.Chem.Soc.,Chem.Commun.,. 139-140 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hiroshi Sakiyama: "Conformationーcontrole in Planar Metal Complexes of Ethylenediamine Derivatives with a Chiral NーSubstituent and Interpretation of CD Spectra Based on Regional Rule" Inorg.Chim.Acta,. 162. 65-70 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Naohisa Kumagai: "Cobalt(III) Mixedーchelates with Tetradentate N,N′ーBis(1ーlーMenthyloxyー3ーbenzoylacetone)ethylenediimine and Bidentate Chelate.Controle of Chelate Conformation by Bidentata Ligand" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 17(1). 69-72 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toshirou Kamiusuki: "Binuclear Copper(II) Complexes of New Dinucleating Ligands with a Pyrazolate Group as an Endogenous Bridge.Effects of Exogenous Azide and acetate Bridge on Magnetic Properties" J.Chem.Soc.,Dalton Trans.,. 2077-2081 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masayuki Koikawa: "Synthesis,Structure,and Redox Properties of Dicopper(II,II) Complexes of Nー(2ーHydroxyphenyl)salicylamide and Homologues.Facile Oxidation to Dicopperー(II,III) and ー(III,III) Species" J.Chem.Soc.,Dalton Trans.,. 2089-2094 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hisashi Okawa: "Synthesis,Structure,and Spectral and Magnetic ProPerties of Trinuclear Copper(II) Complexes bridged by Glyoximate Groups" J.Chem.Soc.,Dalton Trans.469-475 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masahito Kodera: "Binuclear Nickel(II) Complexes of Ditopic Ligands,N,N′ーBis(5ーaminoー3ーhydroxyphenyl)malonamide and N,N′ーBis(5ーaminoー2ーhydroxyphenyl)ー2′ーmalonamide" 九州大学理学部紀要. 17(2). 213-220 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hiroshi Sakiyama: "Tetrahedral Zinc(II) Complex of Nー(R)ー1ーPhenylethylーsalicylaldimine.Structural and CD Spectral Investigations on Stereoselectivity" J.Chem.Soc.,Dalton Trans.2935-2939 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuichiro Aratake: "Cobalt(II)ーLanthanoid(III)(Ln=La,Nd,or Gd)Complexes of N,N′ーEthylenedis(3ーcarboxysalicylideneimine).Interaction of Ligating Groups on the CoーLu Centre" J.Chem.Soc.,Dalton Trans.2941-2945 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Dominique Luneau: "Synthesis,Structure,and Magnetism of Binuclear Cu(II)Cu(II),Cu(II)Ni(II),and Ni(II)Ni(II) Complexes Doubly Bridged by Oximate Groups" Bull.Chem.Soc.Japan. 63. 2212-2217 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Makoto Tadokoro: "Template Synthesis and Crystal Structure of a Dilead(II) Complex of a Macro cycle with NCC4DDOCC2DD Donor Set" Bull.Chem.Soc.Jpn.,. 63. 3337-3339 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kenji Shindo: "Synthesis and Properties of Binuclear M(II)ーdimethylSn(IV) M=Cu,Co) Complexes of N,N′ーBis(3ーcarboxyーsalicylidene)ethylenediamine" Inorg.Chim.Acta,.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toshirou Kamiusuki: "Binuclear Metal(II)(M=Co,Cu) Complexes of 3,5ーBis(N,Nーbis[2ー(diethylamino)ーethyl]aminomethyl}pyrazole" Inor.Chim.Acta,.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. Maeda: "Noncovalent Interactions in Metal Complexes. XI. Synthesis and Stereoselectivity of 1 : 3 Cobalt(III) Complexes of 1-l-Menthyloxy-3-acetylacetone" Polyhedron. 6. 583-586 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Nakamura: "Noncovalent Interactions in Metal Complexes. 14. Proton NMR Spectroscopic Investigation on Stereoselectivity in Co(III) Complexes of Various 3-Substituted 1-Phenyl-1, 3-propanedione" Bull. Chem. Soc. Jpn.60. 539-543 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Okawa: "Noncovalent Interactions in Metal Complexes. 15. Stereoselectivity of Cobalt(III) Mixed Chelates with Bis(1-l-menthyloxy-3-benzoylacetone)ethylenediamine and a Diamine" Inorg. Chim. Acta. 128. 155-159 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Horiuchi: "Cobalt(III) Complexes of Salen Analog with Thioether Pendant Group. X-Ray Structure Analysis and Thioether Coordination Effect" Bull. Chem. Soc. Jpn.60. 3575-3580 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Sakamoto: "Copper(II)-Lanthanoid(III) Complexes of Binucleating Ligands Derived from 3-Formylsalicylic Acid and Diamines" Bull. Chem. Soc. Jpn.61. 1613-1618 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Sakamoto: "Specific Binding of Substrates Containing Nitrogen and Oxygen Donor Groups to Copper(II)-Gadolinium(III) Hetero-metal Center" Bull. Chem. Soc. Jpn.61. 3319-3320 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Okawa: "Noncovalent Interactions in Metal Complexes" Coord. Chem. Rev.92. 1-28 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Okawa: "Noncovalent Interactions in Metal Complexes. 18. Stereoselectivity of 1 : 3 Complexes of Sc, Y, La, Al, Ca, In Ions with 4-(l-Menthyloxy)-1-phenyl-1, 3-butanedione and 4-(lーMenthyloxy)-1-p-tolyl-1.3-butanedione" Inorg. Chem.,. 27. 4373-4377 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Tomita: "Metal Complexes (Co^<3+> , Fe^<3+> , Mn^<3+>) of the Quinquedentate Salen Analog, 2-Methyl-4-benzylthio-N, N-butane-1, 2-diylbis(salicylideneimine) : Crystal Structure and Sulphur Coordination Effect" J. Chem. Soc.Dalton Trans.179-184 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Horiuchi: "Cobalt(II) and mu-Oxodiiron(III, IV) Complexes of Salen Analog with Aromatic Thioether Pendant Group, N, N'-Disalicylidene-2-methyl-4-(2-methylthiophenyl)-1, 2-butanediamine" Inorg. Chim. Acta,. 144. 99-103 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Matsumoto: "Synthesis and X-Ray Crystal Structures of an Imidazolate-bridged Polynuclear Copper(II) Complex Exhibiting a Unique Helicoid Structure" J. Chem. Soc.Dalton Trans.1943-1948 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Okawa: "Enantioselective Reduction of Ketones on Sterically-controlled Lanthanoid(III) Complexes" J. Chem. Soc.Chem. Commun.139-140 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Sakiyama: "Conformation-control in Planar Metal Complexes of Ethylenediamine Derivatives with a Chiral N-Substituent and Interpretation of CD Spectra Based on Regional Rule" Inorg. Chim. Acta. 162. 65-70 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Kumagai: "Cobalt(III) Mixed-chelates with Tetradentate N, N'-Bis(1-l-Menthyloxy-3-benzoylacetone)ethylenediimine and Bidentate Chelate. Control of Chelate Conformation by Bidentate Ligand" Mem. Fac. Sci. Kyushu Univ., Ser. C. 17(1). 69-72 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Kamiusuki: "Binuclear Copper(II) Complexes of New Dinucleating Ligands with a Pyrazolate Group as an Endogenous Bridge. Effects of Exogenous Azide and acetate Bridge on Magnetic Properties" J. Chem. Soc.Dalton Trans.2077-2081 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Koikawa: "Synthesis, Structure, and Redox Properties of Dicopper(II, II) Complexes of N-(2-Hydroxyphenyl)salicylamide and Homologues. Facile Oxidation to Dicopper-(II, III) and -(III, III) Species" J. Chem. Soc.Dalton Trans.2089-2094 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Okawa: "Synthesis, Structure, and Spectral and Magnetic Properties of Trinuclear Copper(II) Complexes Bridged by Glyoximate Groups" J. Chem. Soc.Dalton Trans.469-475 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kodera: "Binuclear Nickel Complexes of Ditopic Ligands, N, N'-Bis(5-amino-3-hydroxyphenyl)-malonamide and N, N'-Bis(5-amino-2-hydroxyphenyl)-2'-phenylmalonamide" Mem. Fac. Sci., Kyushu Univ., Ser. C.17(2). 213-220 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Sakiyama: "A Tetrahedral Zinc(II) Complex of N-(R)-1-Phenylethylsalicylaldimine. Structural and Circular Dichroism spectral Investigation on Stereoselectivity" J. Chem. Soc.,. Dalton Trans.,. 2935-2939 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Aratake: "Cobalt(II)-Lanthanoid(III) (Ln=La, Nd, or Gd) Complexes of N, N'-Ethylenebis-(3-carboxysalicylideneimine). Interaction of Ligating Groups on the Co-Ln Center" J. Chem. Soc.Dalton Trans.2941-2945 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] D. Luneau: "Synthesis, Structure, and Magnetism of Binuclear Cu(II)Cu(II), Cu(II)Ni(II), and Ni(II)Ni(II) Complexes Doubly Bridged by Oxymate Groups" Bull. Chem. Soc. Jpn.63. 2212-2217 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Tadokoro: "Template Synthesis and Crystal Structure of a Dilead(II) Complex of a Macrocycle with N_4O_2 Donor Set" Bull. Chem. Soc. Jpn.63. 3337-3339 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Shindo: "Synthesis and Properties of Binuclear M(II)-dimethylSn(IV) (M=Cu, Co) Complexes of N, N'-Bis(3-carboxysalicylidene)ethylenediamine" Inorg. Chim. Acta,.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Kamiusuki: "Binuclear Metal(II) (M=Co, Cu) Complexes of 3, 5-Bis{N, N-bis[2-(diethylamino)-ethy1]aminomethyl}pyrazole" Inor. Chim. Acta,.

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-08-12  

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