Preparation, resolution, and spectroscopic properties of bis((2-aminoethyl)diphenylphosphine)- and (ethylenediamine)(1,2-bis(diphenylphosphino)ethane)-cobalt(III) complexes of acetylacetonate, malonate, oxalate, and carbonate ions.

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概要

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• New complexes of the [Co(O–O)(edpp)2]- and [Co(O–O)(en)(dppe)]- type were prepared from <I>trans</I>(Cl, Cl)[CoCl<SUB>2</SUB>(edpp)<SUB>2</SUB>]ClO<SUB>4</SUB> and <I>trans</I>-[CoCl<SUB>2</SUB>(en)(dppe)]ClO<SUB>4</SUB>·H<SUB>2</SUB>O, respectively, where O–O is an acetylacetonate, malonate, oxalate, or carbonate ion, and en, edpp, and dppe denote ethylenediamine, (2-aminoethyl)diphenylphosphine, and 1,2-bis(diphenylphosphino)ethane, respectively. All the complexes of the former type gave two geometrical isomers of trans(P, P) and trans(P, N) configurations, which were assigned on the basis of the <SUP>1</SUP>H and <SUP>3</SUP>C NMR, and electronic absorption spectra. No trans(N, N) isomers were formed. The yields of the trans(P, N) isomers were always larger than those of the corresponding trans(P, P) isomers. With the decreasing ring members of the O–O chelates, the yield of the trans(P,P) isomer decreases, the trans(P,P)-carbonato complex being formed in trace amounts. The first absorption bands of the trans(P,P) isomers have very strong intensity as compared with those of the corresponding trans(P,N) and the dppe complexes. All the complexes except for [Co(O–O)(en)(dppe)]<SUP>+</SUP> (O–O=malonate and oxalate ions) were resolved by the chemical or SP-Sephadex C-25 column chromatographic method, and the circular dichroism spectra were recorded and compared with those of related complexes.

• 公益社団法人 日本化学会の論文

著者

• Kashiwabara Kazuo

  Department Of Chemistry Faculty Of Science Nagoya University

• Kinoshita Isamu

  Department Of Chemistry Graduate School Of Science Osaka City University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Atoh Masamichi

  Department of Chemistry, Faculty of Science, Nagoya University

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