Complexes. Author(s): Éva Balogh-Hergovich, József Kaizer, József Pap, Gábor
Speier,* Gottfried Huttner, László. Zsolnai. Ref. No.: I02087 ...
Eur. J. Inorg. Chem. 2002 · © WILEY-VCH Verlag GmbH, 69451 Weinheim, 2002 · ISSN 1434–1948 SUPPORTING INFORMATION Title: Copper-Mediated Oxygenolysis of Flavonols via Endoperoxide and Dioxetan Intermediates; Synthesis and Oxygenation of [Cu II(Phen) 2(Fla)]ClO4 and [Cu II(L)(Fla)2] [FlaH = Flavonol; L = 1,10Phenanthroline (Phen), 2,2'-Bipyridine (Bpy), N,N,N',N'-Tetramethylethylenediamine (TMEDA)] Complexes Author(s): Éva Balogh-Hergovich, József Kaizer, József Pap, Gábor Speier,* Gottfried Huttner, László Zsolnai Ref. No.: I02087
Supporting information
Copper-mediated Oxygenolysis of Flavonols via Endoperoxide and Dioxetan Intermediates;
Synthesis
and
Oxygenation
of
[CuII(phen)2(fla)]ClO4
and
[CuII(L)(fla)2] [flaH = flavonol; L = 1,10-phenanthroline (phen), 2,2’-bipyridine (bpy), N,N,N’,N’-tetramethylethylenediamine (tmeda)] complexes Éva Balogh-Hergovich,[a] József Kaizer,[a] József Pap,[b] Gábor Speier,*[b] Gottfried Huttner[c] and László Zsolnai[c] [a] Research Group for Petrochemistry, Hungarian Academy of Sciences, 8201 Veszprém, Hungary, [b] Department of Organic Chemistry, University of Veszprém, 8201 Veszprém, Hungary, [c] Anorganisch Chemisches Institut, Universität Heidelberg, D-69120 Heidelberg, Germany
Table S1. Kinetic data for the oxygenation of [CuII(L)(fla)2] (7-9) in DMF solution
Figure S1. Plot of initial oxygenation rate of Cu(phen)(fla)2 vs the initial Cu(phen)(fla)2 concentration (experiments 1-8, Table S1).
Figure S2. Eyring plot of the oxygenation of Cu(phen)(fla)2.
Table S1. Kinetic data for the oxygenation of [CuII(L)(fla)2] (7-9) in DMF solution ________________________________________________________________________ Expt. Temp./103[O2]/ 104[Cu]a/ 104k’phen/ Rb/ 10kphen/ 107-d[Cu]/dt °C no. mol dm-3 mol dm-3 s-1 % s-1 mol-1 dm3 mol dm-3 s-1 _________________________________________________________________________________ 1 80 6.91 0.81 7.19 99.82 1.04±0.04 0.572 2 80 6.91 1.32 7.89 99.36 1.14±0.06 0.907 3 80 6.91 1.85 5.17 99.39 0.75±0.02 1.202 4 80 6.91 2.34 5.09 99.10 0.74±0.08 1.395 5 80 6.91 3.14 7.25 99.38 1.05±0.03 2.154 6 80 6.91 3.40 6.42 98.98 0.93±0.10 2.221 7 80 6.91 4.11 7.28 99.09 1.05±0.08 2.912 8 80 5.18 3.80 5.94 98.88 1.15±0.11 9 80 4.61 4.29 4.92 99.58 1.07±0.04 10 80 2.30 4.26 3.32 99.32 1.44±0.05 11 80 1.38 4.29 1.93 98.92 1.56±0.19 0.95±0.06c 12 75 6.70 3.46 4.36 99.43 0.65±0.03 13 85 7.24 4.46 10.95 99.87 1.51±0.06 14 90 7.57 4.01 16.09 99.13 2.13±0.18 d 15 80 1.38 4.29 0.99 99.49 0.72±0.03 e 16 80 1.38 4.29 2.18 99.40 1.58±0.07 f 17 80 1.38 4.29 3.37 99.15 2.44±0.15 g 18 80 6.91 4.20 1.64 99.35 0.24±0.01 h 19 80 6.91 4.20 1.43 99.52 0.20±0.01 ________________________________________________________________________ [a] In 50 cm3 DMF. [b] Correlation coefficients of least-squares regressions. [c] Mean value of the kinetic constant k and its standard deviation σ(k) were calculated as k = (•iwiki/•iwi) and σ (k) = (•iwi(ki-k)2/(n-1)•iwi)1/2, where wi =1/σi2. d7d. e7c. f7b. g8. h9.
3.5 3 2.5 2 1.5 1 0.5
7
-10 (d[Cu(phen)(fla) 2]/dt) 0 / Ms
-1
Figure S1
0 0
1 2 3 4 4 10 [Cu(phen)(fla) 2]0 / M
5
Figure S2
-3.2 -3.3
log k /T
-3.4 -3.5 -3.6 -3.7 -3.8 2.74 2.76 2.78 2.8 2.82 2.84 2.86 2.88 3
-1
-1
(10 T ) / K
