Preparation and characterization of (CoX2(edpp)2)+(edpp=NH2CH2CH2P(C6H5)2,X=Cl-,Br-,I-,NCO-,NCS-,N3-,NO2-) and (CoX2(en)(dppe))+(en=NH2CH2CH2NH2,dppe=(C6H5)2PCH2CH2P(C6H5)2,X=Cl-,Br-,NCS-). Crystal structures of trans(NCS,NCS),cis(P,P)-(Co(NCS)2(edpp)2)Br

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概要

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• Dianionocobalt(III) complexes of the [CoX<SUB>2</SUB>(edpp)<SUB>2</SUB>]<SUP>+</SUP>-type (X=Cl<SUP>−</SUP>, Br<SUP>−</SUP> I<SUP>−</SUP>, NCO<SUP>−</SUP>, NCS<SUP>−</SUP>, N<SUB>3</SUB><SUP>−</SUP>, NO<SUB>2</SUB><SUP>−</SUP>) have been prepared, where edpp is (2-aminoethyl)diphenylphosphine. The corresponding [CoX<SUB>2</SUB>(en)(dppe)]<SUP>+</SUP> complexes are rather unstable and have been obtained only for X=Cl<SUP>−</SUP>, Br<SUP>−</SUP>, and NCS<SUP>−</SUP>, where en and dppe denote ethylenediamine and 1,2-bis(diphenylphosphino)ethane, respectively. Except for the NCS<SUP>−</SUP> complex of edpp, only one geometrical isomer has been obtained for all the complexes. Two geometrical isomers of [Co(NCS)<SUB>2</SUB>(edpp)<SUB>2</SUB>]<SUP>+</SUP> have been isolated, and crystal structures of <I>trans</I>(NCS,NCS),<I>cis</I>(P,P)-[Co(NCS)<SUB>2</SUB>(edpp)<SUB>2</SUB>]Br·3H<SUB>2</SUB>O·(CH<SUB>3</SUB>)<SUB>2</SUB>CO and <I>cis</I>(NCS,NCS),<I>trans</I>(P,P)-[Co(NCS)<SUB>2</SUB>(edpp)<SUB>2</SUB>]Br·CH<SUB>3</SUB>OH have been determined by X-ray analyses. The NCS<SUP>−</SUP> ions in these complexes coordinate to the cobalt(III) ion through their nitrogen atoms with nearly linear Co–N–C–S fragments. The Co–P distances in the isomers are similar to one another, but the average Co–NH<SUB>2</SUB> and Co–NCS distances in the <I>trans</I>(NCS,NCS) isomer (2.010 and 1.882 Å) are longer and shorter than those of the <I>cis</I>(NCS,NCS) isomer (1.970 and 1.960 Å), respectively. Absorption spectra of all the complexes in solution have been recorded and the results compared with those of related dianionocobalt(III) 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

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Ito Tasuku

  Division of Applied Molecular Science, Institute for Molecular Science

• Ito Haruko

  Division of Applied Molecular Science, Institute for Molecular Science

• Atoh Masamichi

  Department of Chemistry, Faculty of Science, Nagoya University

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