Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Analytical and Inorganic
Synthesis and Characterization of Polynuclear Chain and Tetranuclear Complexes of Mixed-Valent Ruthenium(II,III) Pivalate with N,N′-Didentate Ligands
Daisuke YoshiokaMasahiro MikuriyaMakoto Handa
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2004 Volume 77 Issue 12 Pages 2205-2211

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Abstract

Polymeric chain complexes, [Ru2(piv)4(pyz)]n(BF4)n·3nH2O (1), [Ru2(piv)4(4,4′-bpy)]n(BF4)n·nH2O (2), [Ru2(piv)4(dabco)]n(BF4)n·2nH2O (3), [Ru2(piv)4(phz)]n(BF4)n (4), and [Ru2(piv)4(H2O)2(tmpyz)]n(BF4)n·nCH2Cl2 (6), (Hpiv = pivalic acid, pyz = pyrazine, 4,4′-bpy = 4,4′-bipyridine, dabco = 1,4-diazabicyclo[2.2.2]octane, phz = phenazine, and tmpyz = tetramethylpyrazine), were synthesized and characterized by elementary analyses, infrared and electronic spectroscopies, and variable-temperature magnetic susceptibilities (4.5–300 K). A tetranuclear complex, [{Ru2(piv)4(H2O)}2(phz)](BF4)2 (5), was also synthesized, and a “dimer of dimers” structure was confirmed by an X-ray structure analysis. The crystal structure of 6 shows that [Ru2(piv)4(H2O)2]+ units are linked by hydrogen bonds with tmpyz molecules, giving zigzag chains with Ru1–O5···N1 angle of 108.1(2)°. A red-shift of the δ**(Ru2) → σ*(Ru–O), and δ(Ru2) → δ*(Ru2) transition bands of the RuII,III2 core was observed in polymeric chain adducts 14. All of the present complexes show a very weak antiferromagnetic interaction between the dinuclear units with a considerable zero-field splitting parameter.

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© 2004 The Chemical Society of Japan
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