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

0443986 - ÚFCH JH 2016 RIV DE eng J - Článek v odborném periodiku
Bach, M. - Roy, S. - Sarkar, B. - Bubrin, M. - Niemeyer, M. - Fiedler, Jan - Duboc, C. - Kaim, W.
Heterotetranuclear Complexes of Reduced and Non-reduced Bridging 1,2,4,5-Tetrazine Ligands 1,1 '-Bis(diphenylphosphanyl)-ferrocene-copper(I).
Zeitschrift für anorganische und allgemeine Chemie. Roč. 641, č. 2 (2015), s. 327-331. ISSN 0044-2313. E-ISSN 1521-3749
Institucionální podpora: RVO:61388955
Klíčová slova: crystal structure * copper * EPR spectroscopy
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 1.261, rok: 2015

The complexes ((mu-bptz)]Cu(dppf)](2)}(BF4)(2)[(1)(BF4)(2)] [bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, dppf = 1, 1'-bis(diphenyl-phosphanyl)ferrocene] and ((mu-bpztz)[(mu-bptz)]Cu(dppf)](2)}(PF6)(2) [(2)(PF6)(2)] [bpztz = 3,6-bis(2-pyrazinyl)-1,2,4,5-tetrazine] contain two redoxactive heterodinuclear (FPCuI)-Cu-II moieties, bridged by a redox-active ligand. A crystal structure determination of (1)(BF4)(2)center dot 2CH(2)Cl(2) 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 ((mu-bptz)]Cu(dppf)](2)}(+) (1(+)) and ((mu-bpztz)]Cu(dppf)](2)}(+) (2(+)), which could he isolated [as (1)(BF4)] and studied by variable frequency EPR to provide hyperfine (9.5 GHz) and g anisotropy information (285 GHz). Cyclic vollammetry and UV/Vis/NIR spectrodectrochemistry indicate a reversible two-electron oxidation of the well separated (ca. 114 angstrom) ferrocene termini.
Trvalý link: http://hdl.handle.net/11104/0246594