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We encountered similar problems with Cp′2V. However, crystals of Cp′2Cr gave an excellent data set and a good X-ray structure. The Cp′2Cr and Cp′2 Fe crystallize in an orthorhombic crystal lattice, whereas Cp′2Ti and Cp′2V crystallize in a tetragonal lattice: Cp′ 2Ti: a, 12.0614(11) Å, b, 12.0614(11) Å, c =8.5317(11) Å, α, β= γ, 90°; Cp′2V: a, 11.9810(11) Å, b, 11.9810(11) Å, c, 8.6312(11) Å, α, β, γ, 90°; Cp′2Cr: a, 11.7750(6) Å, b, 12.4122(6) Å, c, 32.6410(20) Å, α, β, γ, 90°, Pccn: Schultz, M. Acta Crystallogr. 2007, E63, m3085
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The moment might be low due to the extreme sensitivity of the base-free titanocene to trace amounts of N2 in argon even in the solid state. This is particularly true for those samples that are finely ground, i.e, those used for the magnetic susceptibility measurements
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B is determined in the solid state.
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A referee suggested that the resonance at δ 2.65 may be assigned to the D2h conformer and the one at δ 5.3 to the D2d conformer, since the ratio irreversibly changes toward the δ 5.3 resonance, which is the least sterically congested conformer. Over time, the resonance at δ 2.65 evolved into two resonances, which might be due to various Cp″ ring conformations within the D2h. conformation. While we agree with the general postulate that isomers are present see the next paragraph, we can provide no experimental evidence for the specific assignment. The solid state magnetic measurements might be useful, but they were obtained only to temperatures of 300 K; on cooling from 300 to 5 K, no obvious deviation from the original Χ vs T plots were evident to the eye. We thank a referee for this suggestion
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