0181781 - UFCH-W 20030221 RIV NL eng J - Journal Article
Ye, S. - Kaim, W. - Sarkar, B. - Schwederski, B. - Lissner, F. - Schleid, T. - Duboc-Toia, C. - Fiedler, Jan
First Crystal Structure Determination and High-Frequency EPR Study of an Organoarsanecopper Radical Complex.
Inorganic Chemistry Communications. Roč. 6, - (2003), s. 1196-1200. ISSN 1387-7003. E-ISSN 1879-0259
R&D Projects: GA ČR GA203/03/0821; GA MŠMT OC D15.10
Institutional research plan: CEZ:AV0Z4040901
Keywords : arsane ligands * copper complex * EPR
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 1.513, year: 2003

The red radical complex {(mu-bptz)[Cu(AsPh3)(2)](2)}(BF4) 1, bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, was obtained as a stable species and characterized by X-ray crystallography, spectroelectrochemistry and EPR at 9.5 and 285 GHz. Comparison with the previously reported {(mu-bptz)[Cu(PPh3)(2)](2)}(BF4) 2 reveals longer Cu-element bonds by about 0.1 Angstrom but otherwise a similar "organic sandwich" structure involving intramolecular pi(phenyl)-pi(tetrazine)-pi(phenyl) interactions, a 3+1 coordination at the copper(I) centers, and averaged tetrazine intraring bond distances. Reversible oxidation to a blue dication with an intense MLCT band at 650 nm occurs at -0.24 V vs. Fc(+/o). EPR studies show the effect of the higher spin-orbit coupling constant of the As vs. P atoms through slightly larger g anisotropy as determined through high frequency measurements. (C) 2003 Elsevier B.V. All rights reserved.
Permanent Link: http://hdl.handle.net/11104/0078300