Structural and Magnetic Studies of the Tris(cyclopentadienyl)manganese(II) "Paddle-Wheel" Anions [Cp3−n(MeCp)nMn]− (n=0-3, MeCp=C5H4CH3, Cp=C5H5)

• Published in: Chemistry : a European journal 2006-04, Vol.12 (11), p.3053-3060
• Main Authors: Alvarez, Carmen Soria, Bashall, Alan, McInnes, Eric J. L., Layfield, Richard A., Mole, Richard A., McPartlin, Mary, Rawson, Jeremy M., Wood, Paul T., Wright, Dominic S.
• Format: Article
• Language: English
• Subjects: cyclopentadienyl ligands; magnetic properties; manganese; structure elucidation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200501214

The ion‐contact complexes [{(η5‐Cp)2Mn(η2:η5‐Cp)K}3]⋅0.5 THF (1⋅0.5 THF) and [{(η2‐Cp)2(η2;η5‐MeCp)MnK(thf)}]⋅2 THF (2⋅2 THF) and ion‐separated complexes [Mg(thf)6][(η2‐Cp)3Mn]2 (3), [Mg(thf)6][(η2‐Cp)(η2‐MeCp)2Mn)]2⋅0.5 THF (4⋅0.5 THF), [Mg(thf)6][(η2‐MeCp)3Mn)]2⋅0.5 THF (5⋅0.5 THF) and [Li([12]crown‐4)]5[(η‐Cp)3Mn]5 (6) (Cp=C5H5, CpMe=C5H4CH3), have been prepared and structurally characterised. The effects of varying the Cp and CpMe ligands in complexes 1–5 have been probed by variable‐temperature magnetic susceptibility measurements and EPR spectroscopic studies. Making contact! A series of complexes containing ion‐separated and ion‐paired [Cp3−x(CpMe)xMn]− ions have been structurally characterised. The ion‐paired complexes, which form similar graphite‐like lattices with K+ counterions, are composed of six‐membered K3Mn3 ring units linked by cyclopentadienyl ligands (see picture). The electronic and magnetic properties are investigated by using variable‐temperature magnetic measurements and ESR spectroscopy.