The structure and properties of (.ETA.-cyclopentadienyl)(O-methyl dithiocarbonato)(triphenylphosphine)nickel(II).

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概要

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• The title complex was synthesized, and the structure was determined by means of the X-ray diffraction technique. The crystal is triclinic; space group P\bar1, <I>a</I>=9.944(1), <I>b</I>=14.336(2), <I>c</I>=9.759(1) Å, α=107.00(1), β=117.35(1), γ=76.55(1)°, <I>Z</I>=2, <I>D</I><SUB>x</SUB>=1.40, <I>D</I><SUB>m</SUB>=1.36(3) g cm<SUP>−3</SUP>, μ(Mo <I>K</I>α)=1.08 mm<SUP>−1</SUP>. The <I>O</I>-methyl dithiocarbonato ion acts as a unidentate ligand, and it is coordinated with the metal through one sulfur atom. The coordination number of the metal is 3 if the cyclopentadienyl is regarded as a unidentate ligand. A series of [(η-cyclopentadienyl)(<I>O</I>-alkyl dithiocarbonato)(trialkyl- or triarylphosphine)nickel(II)], [Ni(C<SUB>5</SUB>H<SUB>5</SUB>)(S<SUB>2</SUB>COR)(PR′<SUB>3</SUB>)], where R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, CH<SUB>3</SUB>(CH<SUB>2</SUB>)<SUB>2</SUB>, (CH<SUB>3</SUB>)<SUB>2</SUB>CH, or CH<SUB>3</SUB>(CH<SUB>2</SUB>)<SUB>3</SUB>; R′=C<SUB>6</SUB>H<SUB>5</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB>, or CH<SUB>3</SUB>(CH<SUB>2</SUB>)<SUB>3</SUB>, were also obtained. The dissociation of the phosphine ligand of the complexes in solution was studied spectrophotometrically, and it was found that the more electron-donative the alkyl group of the <I>O</I>-alkyl dithiocarbonato ligand is, the weaker the phosphorus-nickel bond is.

• 公益社団法人 日本化学会の論文

著者

• SATO Shoichi

  The Institure for Solid State Physics, The University of Tokyo

• Shimoi Mamoru

  Department Of Basic Science Graduate School Of Arts And Sciences The University Of Tokyo

• Saito Yoshihiko

  The Institute for Solid State Physics The University of Tokyo

• Ouchi Akira

  Department of Chemistry, College of Arts and Sciences, The University of Tokyo

• Shimoi Mamoru

  Department of Chemistry, College of General Education, The University of Tokyo

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