Electronic absorption, magnetic circular dichroism, and circular dichroism spectra of cis- and trans-(Pd(Cl)2(N)2)-type complexes and their electronic structures.

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概要

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• The electronic absorption and MCD spectra of [PdCl<SUB>2</SUB>L] (L=ethylenediamine(en), 1,3-propanediamine, <I>N</I>,<I>N</I>-dimethylethylenediamine, <I>N</I>,<I>N</I>′-dimethylethylenediamine, <I>N</I>,<I>N</I>-diethylethylenediamine, and <I>N</I>,<I>N</I>-dimethyl-1,3-propanediamine) and <I>trans</I>-[PdCl<SUB>2</SUB>(L)<SUB>2</SUB>] (L=EtNH<SUB>2</SUB>, Me<SUB>2</SUB>NH, Me<SUB>3</SUB>N, <I>n</I>-BuNH<SUB>2</SUB>, <I>i</I>-BuNH<SUB>2</SUB>, <I>s</I>-BuNH<SUB>2</SUB>, <I>t</I>-BuNH<SUB>2</SUB>, and <I>rac</I>-pea (pea=1-phenylethylamine)), and CD spectra of [PdCl<SUB>2</SUB>L] (L=(<I>S</I>)-1,2-propanediamine-(<I>S</I>-pn) and (2<I>S</I>)-<I>N</I><SUP>1</SUP>,<I>N</I><SUP>1</SUP>-diethyl-1,2-propanediamine) and <I>trans</I>-[PdCl<SUB>2</SUB>(<I>S</I>-pea)<SUB>2</SUB>] have been measured over the visible-near UV region, together with the corresponding spectra of [PtCl<SUB>2</SUB>L] (L=en and <I>S</I>-pn). The examination of the three kinds of spectra as well as their Gaussian analyses indicates that the splitting pattern of metal d orbitals for the cis type complexes is similar to that for [PdCl<SUB>4</SUB>]<SUP>2−</SUP>, and that as to the trans complexes the <I>d</I><SUB>x<SUP>2−</SUP>y<SUP>2</SUP></SUB>←<I>d</I><SUB>xz</SUB> and <I>d</I><SUB>yz</SUB> transitions split largely to give apparent two spin-allowed d-d bands characteristic of the trans complexes. The average energy of the <I>d</I><SUB>x<SUP>2−</SUP>y<SUP>2</SUP></SUB>←<I>d</I><SUB>xz</SUB> and <I>d</I><SUB>yz</SUB> transitions for the trans complexes is approximately equal to the energy of the <I>d</I><SUB>x<SUP>2−</SUP>y<SUP>2</SUP></SUB>←<I>d</I><SUB>xz,yz</SUB> (D<SUB>4h</SUB>) ones for the cis complexes. The transition energies of <I>d</I><SUB>x<SUP>2−</SUP>y<SUP>2</SUP></SUB>←<I>d</I><SUB>xy</SUB> and <I>d</I><SUB>x<SUP>2</SUP></SUB> do not differ largely between both types of complexes. The assignments of high-intensity bands have also been made tentatively.

• 公益社団法人 日本化学会の論文

著者

• Komorita Takashi

  Department Of Chemistry Faculty Of Science Osaka University

• Nakayama Kazuhiko

  Department Of Psychiatry Jikei University School Of Medicine

• Shimura Yoichi

  Department of Chemistry Faculty of Science Osaka University

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