Article,

Tetrazine derived mononuclear RuII(acac)2(L) (1), RuII(bpy)2(L)(ClO4)2 (2) and RuII(bpy)(L)2(ClO4)2 (3) (L = 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine, acac = acetylacetonate, bpy = 2,2'-bipyridine): Syntheses, structures, spectra and redox properties

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Polyhedron, 24 (2): 333--342 (2005)
DOI: 10.1016/j.poly.2004.11.019

Abstract

Mononuclear Ru complexes of tetrazine derived L, RuII(acac)2(L) (1), RuII(bpy)2(L)(ClO4)2 (2) and RuII(bpy)(L)2(ClO4)2 (3) (L = 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine) were prepd. The free L exists as a dimeric entity in the solid state via H bonding interactions involving L and H2O mols. present in the crystal lattice. 1 Exhibits unusually strong bonds from RuII to coordinating pyrazolyl-N (2.040(2) \AA) and esp. to tetrazine-N (1.913(2) \AA). The RuIII/RuII couples of 1-3 appeared at 0.28, 1.34 and 1.50 V vs. SCE, resp. The tetrazine and bpy-based redns. were obsd. at -1.33 (1); -0.55 and -1.55/-1.75/-1.98 (2); -0.47/-0.78 and -1.80/-2.02 V (3), resp. 1, 2 And 3 displayed two MLCT bands each, corresponding to dp(RuII) $\rightarrow$ p* (L, tetrazine) and dp(RuII) $\rightarrow$ p* (acac or bpy or L) transitions. 1+ And 2+ showed rhombic EPR spectra at 110 and 4 K, resp. and 1-, 2- and 3- exhibited multiple line EPR spectra at 300 K 1-3 exhibited moderately strong emission spectra in EtOH-MeOH glass at 77 K. on SciFinder(R)

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