Stereochemistry of alkyl pendant ligands coordinated to metal complexes and its effect on reactivity

• Project/Area Number: 04640583
• Research Category: Grant-in-Aid for General Scientific Research (C)
• Allocation Type: Single-year Grants
• Research Field: 無機・錯塩・放射化学
• Research Institution: Kumamoto University
• Principal Investigator: GOTO Masafumi Kumamoto University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (50080180)
• Co-Investigator(Kenkyū-buntansha): KUROSAKI Hiromasa Kumamoto University, Faculty of Pharmaceutical Sciences, Asistant Professor, 薬学部, 助手 (70234599) ; MORI Hiromasa Kumamoto University, Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (40040315)
• Project Period (FY): 1992 – 1993
• Project Status: Completed (Fiscal Year 1993)
• Budget Amount: ¥1,900,000 (Direct Cost: ¥1,900,000); Fiscal Year 1993: ¥400,000 (Direct Cost: ¥400,000); Fiscal Year 1992: ¥1,500,000 (Direct Cost: ¥1,500,000)
• Keywords: Fe complexes / cobalt(III)complexes / platinum(II) complexes / dehydrogenation / hydrophobic interaction / NMR / X-ray crystallography / alkyl pendant ligand / N-ベンジルエチレンジアミン / 配位原子 / アルキルペンダント / 金属錯体

Research Abstract

The Co, Fe, and Pt complexes containing the alkyl pendant ligands were synthesized and their characteristics were clarified.
1. N-Alkyl substituents of [Co^<III>(CN)_4L]^<3+> or [Co^<III>(NH_3)_4L]^<3+>(L=Eten or Been) took pseudoequatorial disposition in regard with the chalete ring and anti-conformation. N-Benzyl group of [Pt(bpy)L]^<2+> and [Pt(bpy)L]^<2+> took pseudoaxial disposition and a intramolecular hydrophobic interaction occurred between the aromatic rings in aqueous solution. Substitution of N-benzyl with N-naphthylmethyl and N-anthrylmethyl in the ternary Pt^<II> enhanced the intramolecular interaction. In both aqueous solution and crystals, the pendants took -syn -conformation which was supported by a molecular mechanics calculation. Intramolecular hydrophobic interaction of these complexes were weakened by addition of nonpolar solvents or protein denaturants such as urea.
2. The oxidation of [Fe^<II>(CN)_4(Been)] with H_2O_2 yielded consecutively the monoimine and the diimine complexes. This was due to the enhanced reactivity at the secondary amine. The monoimine complex was isolated for the first time from the diamine complex by using this dehydrogenation.
3. Intramolecular interaction between aromatic rings in Pt^<II> complexes of bpy and N-omega-phenyl-alkylethylenediamine with variation of the number of methylene brige(n) 1 to 5, was most strengthened with n=1. The intermolecular interaction between these complexes and aromatic sulfonate was most strengthened with n=3.

Research Products

• [Publications] Reiko Saito: "Diastereoisomers of Platinum(II)Complexes with Chiral N-Substituted 1,2-Diamines.I.Structure and Isomerization of Dichloro{(R)-2-[(2-methyl-2-aminopropyl)amino]-1-butanol}platinum(II)" Bull.Chem.Soc.Jpn.65. 1428-1437 (1992)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Reiko Saito: "Diastereoisomers of Platinum(II)Complexes with Chiral N-Substituted 1,2-Diamines.II.Structure and Dichloro[(S)-1-(2-amino-2-methylpropyl)amino-2-butanol]platinum(II)" Bull.Chem.Soc.Jpn.65. 2118-2126 (1992)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Reiko Saito, Masafumi Goto, Junzo Hirose, and Yoshinori Kidani: "Diasteromers of Platinum(II) complexes with Chiral N-Substituted 1,2-Diamines. I.Structure and Isomerization of Dichloro {(R)-2-[(2-methyl-2-aminopropyl)amino]-1-butanol} plathnum(II)" Bull.Chem.Soc.Jpn.65(5). 1428-1437 (1992)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Reiko Saito, Masafumi Goto, Junzo Hirose, and Yoshinori Kidani: "Diasteromers of Platinum(II) complexes with Chiral N-Substituted 1,2-Diamines. II.Structure of Dichloro [(S)-1-[(2-amino-2-methyopropyl)amino-2-propanol] plathnum(II)" Bull.Chem.Soc.Jpn.65(8). 2118-2126 (1992)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Reiko Saito: "Diasteromers of Platinum(II)complexes with Chiral N-Substituted 1,2-Diamines.I.Structure and Isomerization of Dichloro{(R)-2-[(2-methyl-2-aminopropyl)amino]-1-butanol} platinum(II)" Bull.Chem.Soc.Jpn.,. 65. 1428-1437 (1992)
• [Publications] Reiko Saito: "Diasteromers of Platinum(II)complexes with Chiral N-Substituted 1,2-Dimines.II.Structure of Dichloro[(S)-1-(2-amino-2-methylpropyl)amino-2-propanol] platinum(II)" Bull.Chem.Soc.Jpn.,. 65. 2118-2126 (1992)
• [Publications] Masafumi Goto: "Diastereoisomers of Platinum(II) Compleres with Chirol N-Subustituted 1,2-Diamines.I.Structure and Isomerization of Dichloroi(R)-2-[methy1-2-aminopropyl)amino]-1-butanoly platinum(II)" Bull.Chem.Soc.Jpn.65. 1428-1437 (1992)
• [Publications] Masafumi Goto: "Diasterecistmers of Platinum(II) Compleces with Chiral N-Subustitubed 1,2-Diamines II.Structures of Dichloro [(S)-1-(2-amino-2-methyl prophyl)amino-2-propanol]Platinum(II)" Bull.Chem.Soc.Jpn.65. 2118-2126 (1992)