Article,

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

Abstract

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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