Heterotetranuclear Complexes of Reduced and Non‐reduced Bridging 1, 2, 4, 5‐Tetrazine Ligands with 1, 1′‐Bis(diphenylphosphanyl)‐ferrocene‐copper(I)12. Issue 2 (30th January 2015)

• Record Type: Journal Article
• Authors: Bach, Monika; Roy, Sayak; Sarkar, Biprajit; Bubrin, Martina; Niemeyer, Mark; Fiedler, Jan; Duboc, Carole; Kaim, Wolfgang
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 641:Issue 2(2015)
• Page Start: 327
• Page End: 331
• Publication Date: 2015-01-30
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201400564
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The complexes {(μ‐bptz)[Cu(dppf)]₂}(BF₄)₂ [(<bold>1</bold>)(BF₄)₂] [bptz = 3, 6‐bis(2‐pyridyl)‐1, 2, 4, 5‐tetrazine, dppf = 1, 1′‐bis(diphenylphosphanyl)ferrocene] and {(μ‐bpztz)[Cu(dppf)]₂}(PF₆)₂ [(<bold>2</bold>)(PF₆)₂] [bpztz = 3, 6‐bis(2‐pyrazinyl)‐1, 2, 4, 5‐tetrazine] contain two redox‐active heterodinuclear Fe^IICu^I moieties, bridged by a redox‐active ligand. A crystal structure determination of (<bold>1</bold>)(BF₄)₂<bold>·</bold>2CH₂Cl₂ confirms the non‐reduced aromatic nature of the bridge, in contrast to previous results on dicopper(I) complexes of bptz. Facile one‐electron reduction produces the radical complexes {(μ‐bptz)[Cu(dppf)]₂}⁺ (<bold>1</bold>⁺) and {(μ‐bpztz)[Cu(dppf)]₂}⁺ (<bold>2</bold>⁺), which could be isolated [as (<bold>1</bold>)(BF₄)] and studied by variable frequency EPR to provide hyperfine (9.5 GHz) and <italic>g</italic> anisotropy information (285 GHz). Cyclic voltammetry and UV/Vis/NIR spectroelectrochemistry indicate a reversible two‐electron oxidation of the well separated (ca. 13.4 Å) ferrocene termini.</p> </abstract>