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|Title:||Electronic communication in oligometallic complexes with ferrocene-based tris(1-pyrazolyl)borate ligands||Authors:||Guo, S. L.
Fabrizi De Biani, Fabrizia
Bats, J. W.
|Issue Date:||2001||Project:||None||Journal:||INORGANIC CHEMISTRY||Abstract:||
Ferrocene-based tris(1-pyrazolyl)borate ligands 1R−Li and 1R−Tl have been synthesized and used to generate a variety of heterotrinuclear transition metal complexes, 3R−M [R = H, SiMe3, cyclohexyl, (cyclohexyl)methyl, phenyl; M(II) = Mn, Fe, Co, Ni, Cu, Zn]. The poor solubility of 3H−M is greatly enhanced by the introduction of large organic substituents into the 4-positions of all pyrazolyl rings. The unsubstituted ligand 1H−Li and the trinuclear complex 3Cym−Cu [Cym = (cyclohexyl)methyl] have been investigated by X-ray crystallography. 1H−Li, which represents the first example of a structurally characterized lithium tris(1-pyrazolyl)borate, forms centrosymmetric dimers in the solid state. A severe Jahn−Teller distortion was observed for the (Bpz3)2Cu fragment in 3Cym−Cu. Compared to the parent compounds [(HBpz3)2M], the presence of uncharged ferrocenyl substituents in 3R−M tends to shift the M2+/M3+ redox potential to significantly more cathodic values. The opposite is true if the ferrocenyl fragments are in their cationic state, which results in an anodic shift of the M2+/M3+ transition. Most interestingly, the two ferrocenyl fragments in 3R−Cu appear to be electronically communicating.
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