The crystal and molecular structures of trans-dichlorobis(dimethylneomenthylphosphine)palladium(II) and trans-dichlorobis(dimethylmenthylphosphine)palladium(II), asymmetric hydrosilylation catalysts of olefin.

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概要

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• The molecular structures of [PdCl<SUB>2</SUB>{(Me<SUB>2</SUB><I>neo</I>Men)P}<SUB>2</SUB>] and [PdCl<SUB>2</SUB>{(Me<SUB>2</SUB>Men)P}<SUB>2</SUB>], asymmetric hydrosilylation catalysts of olefin, were determined by means of X-ray diffraction. Both complexes form yellow prismatic crystals. The former belongs to the monoclinic system: <I>a</I>=13.512(5), <I>b</I>=13.082(1), <I>c</I>=8.472(1) Å, and β=97.00(2)°, space group P2<SUB>1</SUB> with <I>Z</I>=2; the latter belongs to the tetragonal system: <I>a</I>=9.662(1) and <I>c</I>=32.459(2) Å, space group P4<SUB>3</SUB>2<SUB>1</SUB>2 with <I>Z</I>=4. Both structures were determined by the heavy atom method and have been refined anisotropically by a least-squares procedure (<I>R</I>=0.0697 for 2606 non-zero reflections for the former and <I>R</I>=0.0713 for 1388 non-zero reflections for the latter). The former molecules is not iso-structural with its nickel analog. The central palladium atom has <I>trans</I>-square planar geometry [Pd–Cl 2.304(5) and 2.297(5), Pd–P 2.344(4) and 2.361(5) Å]. The molecule has an approximate two-fold symmetry around the normal to the coordination plane. The neomenthyl groups are on the same side of the co-ordination plane. The latter molecule has exact C<SUB>2</SUB> symmetry: the two-fold axis passes through the Cl(1), Pd, and Cl(2) atoms which lie on the co-ordination plane. The geometry around the palladium slightly deviates from the <I>trans</I>-square planar [Pd–Cl 2.296(9) and 2.267(9) Å and Pd–P 2.310(6) Å]. The menthyl groups are located on either side of the co-ordination plane.

• 公益社団法人 日本化学会の論文

著者

• Miki Kunio

  Department Of Chemistry Graduate School Of Science Kyoto University

• Kai Yasushi

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Kasai Nobutami

  Department Of Applied Biological Science Tokyo University Of Science

• Yasuoka Noritake

  Department Of Life Science Faculty Of Science Himeji Institute Of Technology

• KAI Yasushi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Kan Kojiro

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Miki Kunio

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Yasuoka Noritake

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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