Heterotetranuclear Complexes of Reduced and Non-reduced Bridging 1,2,4,5-Tetrazine Ligands with 1,1'-Bis(diphenylphosphanyl)-ferrocene-copper(I)

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Zeitschrift fuer Anorganische und Allgemeine Chemie, 641 (2): 327--331 (2015)
DOI: 10.1002/zaac.201400564


Complexes (μ-bptz)Cu(dppf)2(BF4)2 (1)(BF4)2 bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, dppf = 1,1'-bis(diphenylphosphino)ferrocene and (μ-bpztz)Cu(dppf)2(PF6)2 (2)(PF6)2 bpztz = 3,6-bis(2-pyrazinyl)-1,2,4,5-tetrazine contain two redox-active heterodinuclear FeIICuI moieties, bridged by a redox-active ligand. A crystal structure detn. of (1)(BF4)2·4CH2Cl2 confirms the nonreduced arom. nature of the bridge, in contrast to previous results on dicopper(I) complexes of bptz. Facile 1-electron redn. produces the radical complexes (μ-bptz)Cu(dppf)2+ (1+) and (μ-bpztz)Cu(dppf)2+ (2+), which could be isolated as (1)(BF4) and studied by variable frequency EPR to provide hyperfine (9.5 GHz) and g anisotropy information (285 GHz). Cyclic voltammetry and UV/visible/NIR spectroelectrochem. indicate a reversible two-electron oxidn. of the well sepd. ($\sim$13.4 \AA) ferrocene termini. on SciFinder(R)



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