Studies on mixed valence complexes of platinum and palladium. II. The crystal structures of [Pt(tn)2][PtCl2(tn)2](BF4)4, [Pt(tn)2][PtBr2(tn)2](ClO4)4, and [Pt(tn)2][PtBr2(tn)2](BF4)4.
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概要
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The crystal structures of Pt(II)–Pt(IV) complexes, [Pt(tn)<SUB>2</SUB>][PtCl<SUB>2</SUB>(tn)<SUB>2</SUB>](BF<SUB>4</SUB>)<SUB>4</SUB> (<B>1</B>), [Pt(tn)<SUB>2</SUB>][PtBr<SUB>2</SUB>(tn)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>4</SUB> (<B>2</B>), and [Pt(tn)<SUB>2</SUB>][PtBr<SUB>2</SUB>(tn)<SUB>2</SUB>](BF<SUB>4</SUB>)<SUB>4</SUB> (<B>3</B>) have been determined by the single-crystal X-ray diffraction method, where tn denotes trimethylenediamine. The crystals of these complexes are isomorphous with one another and the space group is A222 with <I>a</I>=10.790(2), <I>b</I>=13.872(2), <I>c</I>=10.287(1) Å for <B>1</B>, <I>a</I>=11.003(6), <I>b</I>=13.979(6), <I>c</I>=10.355(4) Å for <B>2</B>, and <I>a</I>=10.925(3), <I>b</I>=13.862(3), <I>c</I>=10.291(1) Å for <B>3</B>. The structures were determined by the heavy atom method and refined by the block-diagonal least-squares method to give the disagreement factor 0.082, 0.089, and 0.086 for <B>1</B>, <B>2</B>, and <B>3</B>, respectively. Each crystal comprises infinite Pt<SUP>II</SUP>…X–Pt<SUP>IV</SUP>–X… chains running parallel to the a-axis. In the chain, tetragonal bipyramidal [Pt<SUP>IV</SUP>X<SUB>2</SUB>(tn)<SUB>2</SUB>]<SUP>2+</SUP> (X=Cl or Br) and square planar [Pt<SUP>II</SUP>(tn)<SUB>2</SUB>]<SUP>2+</SUP> units are stacked alternately. Two of the fluorine or oxygen atoms of the counter anion are hydrogen-bonded to the nitrogen atoms of the ligand, contributing to the formation of an infinite chain.
- 公益社団法人 日本化学会の論文
著者
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Yamashita Masahiro
Department Of Bioengineering Tokyo Institute Of Technology
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Kida Sigeo
Department of Chemistry Wakayama University
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Matsumoto Naohide
Department of Applied Chemistry, Faculty of Engineering, Kumamoto University
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Yamashita Masahiro
Department of Chemistry, Faculty of Science, Kyushu University 33
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